J. Anal. Appl. Pyrolysis 80 (2007) 166174 www.elsevier.

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Activated carbons prepared by pyrolysis of mixtures of carbon precursor/alkaline hydroxide

denas *, J.P. Marco-Lozar, D. Cazorla-Amoro s, A. Linares-Solano M.A. Lillo-Ro
mica Inorga nica, Universidad de Alicante, Ap. Correos 99, E-03080 Alicante, Spain Departamento de Qu Received 14 December 2006; accepted 26 January 2007 Available online 3 February 2007

Abstract In the present paper, heat-treatments in N2 atmosphere of mixtures of different precursors and alkaline hydroxides are studied. The paper analyses the effect that the precursors nature (coals, lignocellulosic materials and carbon bre) has on the nal porosity of the resulting activated carbons. The results show that this physical mixing method can be effectively used for all the selected precursors, both with NaOH and KOH. However, differences in adsorption capacity and porosity distribution are observed depending on the precursor and on the hydroxide used. The different behaviour exhibited by both activating agents can be explained by the different structural order in the raw materials. As a general trend, NaOH is more efcient in the activation of low structural-ordered materials, whereas KOH is more effective for the highly ordered materials, what indicates differences in the activation performance of both hydroxides. The results obtained from precursors submitted to a pyrolysis step previous to the heat-treatment of the carbon precursorhydroxide mixtures corroborate the observed tendencies. # 2007 Elsevier B.V. All rights reserved.
Keywords: Activated carbon; Chemical activation; Precursors; Reactivity

1. Introduction Activated carbons (ACs) are very interesting sorbents both for liquid and gaseous phase applications [1,2]. Two different methods can be employed for their preparation: the so-called physical activation and chemical activation [1]. Physical activation is the most widely used, and its performance in many different types of precursors has been carefully analysed in the literature, focusing recently on the activation of lignocellulosic and other waste materials [36]. However, nowadays chemical activation is receiving more attention. This interest is due to some important advantages over the so-called physical activation, such as (i) the heat-treatment stage usually requires lower temperature and shorter time; (ii) it allows to obtain very high surface area activated carbons (ACs) with controlled micropore size distribution (MPSD) and, if desired, a narrow one; (iii) the yields of carbon are usually higher than in physical activation; (iv) the ash content of the precursors is not a drawback, etc.

* Corresponding author. Tel.: +34 965909350; fax: +34 965903454. denas). E-mail address: mlillo@ua.es (M.A. Lillo-Ro 0165-2370/$ see front matter # 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jaap.2007.01.014

Different agents can be used in the chemical activation process. Activation with phosphoric acid is mostly employed for lignocellulosic precursors, focusing recently on the activation of new waste precursors [710], whereas alkaline hydroxides (KOH and NaOH) are being assayed in chemical activation of coals [1118] and lately also in some other precursors [8,19,20]. We have observed that hydroxides activation of anthracite usually carried out impregnating the precursor with a hydroxide solution followed by a heat-treatment can be simplied by a simple physical mixing (direct mixing) of the hydroxide and the precursor and a subsequent heat-treatment. This simple process is useful for KOH and NaOH [18,21,22]. Furthermore, in the case of NaOH the physical mixing method was proved to be more efcient than impregnation [18]. In line with these observations, some other authors have recently used such physical mixing method [23,24], but most of the papers deal with heat-treatment of anthracite and hence there is still lack of information about its possible extension to other precursors, especially lignocellulosic materials. Thus, the purpose of this work is to extend the hydroxides activation by physical mixing method followed by a heattreatment (pyrolysis) to a wide variety of carbonaceous

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precursors including lignocellulosic materials and different rank coals. The pyrolysis conditions for the activation were xed after analysing their effect on the nal porosity of the ACs using a commercial coconut shell as reference. The experimental preparation conditions were kept constant with the purpose of comparing the effect of the precursor. Special attention is directed to the effect of the precursor reactivity on the subsequent porosity development and, for a selected precursor, the comparison of the behaviour of NaOH and KOH as chemical activating agents is carried out. In addition, the effect of a pyrolysis step over the precursor previous to activation will be studied for both lignocellulosic and coal precursors. 2. Experimental 2.1. Precursors characterisation In this work, 16 different carbonaceous precursors were chosen. These precursors were classied in two different groups, coals and other precursors, comprising the pristine and pyrolysed (carbonised) materials. The pristine coal precursors include a lignite (L), two subbituminous coals (SB1 and SB2) and two anthracites (GA, A). CL (prepared from L by pyrolysis up to 850 8C) and A1000 (prepared from A by pyrolysis up to 1000 8C) were selected as pyrolysed coal precursors. The other precursors are eucalyptus wood (EW), coconut shell (CS), almond shell (AS) and carbon bre (CF). A commercial pyrolysed coconut shell (C) and also pyrolysed samples (CCS, CEW and CAS) prepared by pyrolysis up to 850 8C of CS, EW and AS precursors, respectively, were used. Additionally, and in order to analyse the inuence of the thermal treatment on the nal porosity development, coconut

shell (CS) was submitted to a pyrolysis treatment up to 350 8C previous to the activation step. Therefore, two pyrolysis temperatures, 350 and 850 8C, were studied for this precursor. The activation of these samples will be compared to that for the original coconut shell (CS). Tables 1 and 2 summarise the elemental analysis and the ashcontent of the coals and the other precursors, respectively. The ash-content was determined in a mufe by heating in air around 0.5 g of each precursor up to 900 8C, which was held for 10 h. The precursors reactivity with the hydroxides during the heat-treatment was estimated in air, considering previously published results based on the similarities between a carbon gas reaction (carbonair) with a carbonliquid reaction (carbonalkaline hydroxide) [25]. Reactivity in air was estimated by thermogravimetric analysis (TG) using 60 ml min1 air ow rate (heating rate of 5 8C min1 up to 650 8C). Figs. 1 and 2 summarise the TG curves obtained with the precursors used in this study. Table 3 compiles the temperature for a weight loss of the precursor of 20% (T20), as an indication of the precursors air reactivity, which is related to the reactivity during the heat-treatment in presence of alkaline hydroxides. 2.2. Chemical activation The samples activated with either NaOH or KOH were prepared by physical mixing using a hydroxide/precursor ratio of 3/1 (weight terms), following the method used in a previous study of an anthracite activation [18]. To select the most suitable activation conditions (that is heating rate and maximum heat-treatment temperature) the study was focused on a commercial pyrolysed coconut-shell precursor (C) and on NaOH. Pyrolysis was carried out in a horizontal furnace

Table 1 Elemental analysis and ash-content of the coals and pyrolysed coals used as precursors Precursor L SB1 SB2 GA A CL A1000 Carbon (%) 57.3 66.3 68.6 84.1 81.9 83.7 91.2 Nitrogen (%) 0.7 2.0 1.5 1.2 1.4 0.2 0.5 Hydrogen (%) 4.8 4.4 4.4 2.8 3.1 0.4 0.2 Oxygen (%) 37.0 26.4 19.0 11.5 13.1 15.5 7.7 Sulphur (%) 0.2 0.9 6.5 0.4 0.5 0.2 0.4 Ash (%) 2.6 8.0 13.0 9.4 12.5 7.7 15.0

Table 2 Elemental analysis and ash-content of the lignocellulosic precursors, pyrolysed lignocellulosic precursors and the carbon bre Precursor AS CS EW C CEW CAS CCS CF Carbon (%) 47.8 52.4 47.2 85.5 81.1 88.4 94.5 90.9 Nitrogen (%) 0.4 0.4 0.0 0.2 0.0 0.0 0.3 1.2 Hydrogen (%) 6.0 5.7 5.9 2.0 1.7 1.1 0.5 1.0 Oxygen (%) 45.4 41.5 46.9 12.3 16.9 10.0 4.7 6.7 Sulphur (%) 0.4 0.0 0.0 0.0 0.3 0.5 0.0 0.2 Ash (%) 0.1 1.0 1.4 6.0 2.0 0.3 0.6 0.1

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Fig. 3. Effect of the heating rate during pyrolysis on the porosity development (maximum heat-treatment temperature 750 8C). Fig. 1. TG curves in air for the coals and pyrolysed coals used as precursors.

Fig. 2. TG curves in air for the lignocellulosic precursors, pyrolysed lignocellulosic precursors and the carbon bre.

Fig. 4. Comparison between the specic surface areas of ACs prepared at different pyrolysis conditions.

(500 ml min1 N2 ow) maintaining constant the holding time at the maximum heat-treatment (1 h). After heat-treatment, the samples were washed with HCl and distilled water. Figs. 3 and 4 compile the obtained results. 2.3. Porosity characterisation The different ACs were characterised by physical adsorption of gases (N2 and CO2 at 196 and 0 8C, respectively) using an Autosorb 6-B apparatus (Quantachrome Corporation). Nitrogen adsorption at 196 8C has been used for determining the total volume of micropores (pore size smaller than 2 nm)
Table 3 Reactivity for the different precursors used in this study Precursor L SB1 SB2 GA A CL A1000 T (8C) (20% weight loss) 266 438 477 543 582 445 639 Precursor AS CS EW C CEW CAS CCS CF T (8C) (20% weight loss) 284 285 299 451 484 524 529 551

applying the DubininRadushkevich equation and for determining the apparent BET surface area, whereas the adsorption of CO2 at 0 8C has been used to assess the narrowest micropores (pore size smaller than 0.7 nm) also by application of the DubininRadushkevich equation [26,27]. Figs. 5 and 6 present the N2 adsorption isotherms of the ACs prepared by NaOH activation of coals and other precursors,

Fig. 5. N2 adsorption isotherms at 196 8C of activated carbons prepared from coals using NaOH.

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Fig. 6. N2 adsorption isotherms at 196 8C of activated carbons prepared from other precursors using NaOH.

Fig. 8. N2 adsorption isotherms at 196 8C of activated carbons prepared from other precursors using KOH.

respectively. For the activation with KOH, N2 adsorption isotherms are shown in Fig. 7 (coals) and Fig. 8 (other precursors). Porosity characterisation of these materials is summarised in Table 4 (for coal-based AC) and Table 5 (for ACs prepared from other precursors). Tables 4 and 5 also present the activation yield, calculated as the ratio of activated carbon prepared to precursor used in the activation. To study the inuence of the activating agent and the precursor in the porous texture of the prepared activated carbons, the microporosity percentage was estimated from the N2 adsorption data, applying the following equation: % microporosity
Fig. 7. N2 adsorption isotherms at 196 8C of activated carbons prepared from coals using KOH.

V DR N2 100 V N2 P=Po 0:95

In this equation, V DR N2 is the volume of micropores calculated applying the DubininRadushkevich equation to the nitrogen

Table 4 Porosity characterisation for the chemically activated carbons prepared with NaOH or KOH from different coal precursors Precursor L SB1 SB2 GA A CL A1000 NaOH BET (m2 g1) 1731 2372 2137 1741 2208 630 58 DR N2 (cm3 g1) 0.76 0.87 0.81 0.70 0.84 0.26 0.02 DR CO2 (cm3 g1) 0.56 0.59 0.54 0.61 0.72 0.17 0.03 Yield (%) 15 31 26 55 52 41 80 Micro (%) 84 69 81 81 81 55 50 KOH BET (m2 g1) 1594 1846 1988 2430 2746 860 77 DR N2 (cm3 g1) 0.71 0.73 0.77 1.03 0.97 0.36 0.04 DR CO2 (cm3 g1) 0.59 0.61 0.59 0.77 0.77 0.26 0.08 Yield (%) 27 39 42 69 74 60 93 Micro (%) 87 78 74 90 77 70 77

Table 5 Porosity characterisation for the chemically activated carbons prepared with NaOH or KOH from other precursors Precursor AS CS EW C CEW CAS CCS CF NaOH BET (m2 g1) 2073 1998 3167 2196 1830 1140 1155 1512 DR N2 (cm3 g1) 0.83 0.81 1.35 0.92 0.75 0.49 0.51 0.70 DR CO2 (cm3 g1) 0.67 0.56 0.74 0.65 0.63 0.49 0.44 0.60 Yield (%) 5 4 2 57 52 89 72 55 Micro (%) 76 69 67 89 85 89 87 88 KOH BET (m2 g1) 2100 1740 2000 2030 1736 1457 1229 1500 DR N2 (cm3 g1) 0.86 0.74 0.88 0.88 0.79 0.67 0.56 0.69 DR CO2 (cm3 g1) 0.61 0.57 0.67 0.73 0.67 0.67 0.53 0.50 Yield (%) 8 10 4 65 55 76 81 66 Micro (%) 82 78 92 88 95 97 95 97

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precursors, which were divided into two categories: coal precursors and other precursors (including lignocellulosic materials and a carbon bre). Table 1 shows, as expected, that the carbon content in the coal precursors increases with the coal rank and that, independently of the precursor, the carbon content in coals is higher than that in the lignocellulosic materials. Moreover, it can be seen that the carbon bre (compare Tables 1 and 2) has the highest carbon content of the precursors used. The high carbon content of this material can be explained considering its preparation procedure. Presumably, the heat treatment temperature in its preparation is in the range of 1000 8C. Regarding the ash content of the different precursors, Tables 1 and 2 show that the higher ash contents correspond to the coal precursors (with values ranging up to 13.0 wt%), in contrast to those of the lignocellulosic materials and the carbon bre, in all cases lower than 1.5 wt%. Table 3 summarises the reactivity in air of the different precursors used, estimated from the TG curves shown in Figs. 1 and 2. The results for the precursors reactivities are discussed in detail in the following section. 3.1. Effect of the experimental conditions on the activation results In order to x the activation parameters for all the selected precursors, different experimental conditions (i.e. heating rate and nal activation temperature) were studied for a particular precursor, a commercial carbonised coconut shell. This precursor was selected for two main reasons: (i) the lack of experimental data regarding chemical activation by physical mixing of lignocellulosic precursors and (ii) the intermediate reactivity value of this precursor amongst the different materials studied. Sodium hydroxide was selected as activating agent. Fig. 3 shows the effect of the heating rate on the apparent BET surface area of the AC prepared by NaOH activation, at 750 8C heat-treatment temperature. It can be observed that the lower the heating rate used, the higher the specic surface area. Fig. 4 compares the total micropore volume of ACs prepared at three different maximum heat-treatment temperatures, from 650 to 850 8C, using two different heating rates. For all the heat-treatment temperatures assayed, the lower heating rate, 5 8C min1, is more effective. Comparison between pyrolysis temperatures shows that the intermediate temperature, 750 8C, is the most suitable. Therefore, and considering the previous results, 5 8C min1 heating rate and 750 8C maximum heat-treatment temperature were chosen for the preparation of activated carbons. 3.2. Activation of the different precursors Figs. 58 present the N2 adsorption isotherms for the different ACs prepared using the previously mentioned experimental conditions and Tables 4 and 5 compile their porosity characterisation together with the activation yields. These gures and tables show that very different porosity developments and porosity distributions are achieved as a function of the

Fig. 9. DFT porosity distribution of (a) ACs prepared by NaOH or KOH activation of L, (b) ACs prepared by NaOH or KOH activation of SB2 and (c) ACs prepared by NaOH or KOH activation of GA.

adsorption data at 196 8C whereas V N2 P=Po 0:95 is the volume of nitrogen adsorbed at 196 8C and a relative pressure of 0.95. Porosity distributions of the prepared ACs have been assessed by the non-local density functional theory method (NLDFT). Fig. 9 summarises the results obtained, applying the Quantachrome software package supplied with the equipment to the nitrogen adsorption data up to a relative pressure of 0.7, successfully used before in the characterisation of AC materials [28]. 3. Results and discussion The present paper focuses on the activation of a wide variety of carbonaceous precursors with either sodium or potassium hydroxide. Tables 1 and 2 compile the characterisation of these

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precursor and the activating agent. From these data it can be conrmed that chemical activation with both hydroxides (NaOH and KOH) by the physical mixing method can be successfully applied to all the analysed precursors (coals, lignocellulosic materials and bres). Specic surface areas from 58 to 3167 m2 g1 were achieved and ACs with micropore volumes as high as 1.35 cm3 g1 were prepared. The importance of the precursor and the activating agent merits further discussion and will be analysed in the following sections. 3.3. Reactivity of the precursors used in chemical activation The hydroxide activation, as reported previously, is a solid liquid reaction that seems to occur through the following stoichiometric reaction [25,29]: 6MOH 2C $ 2M 3H2 2M2 CO3 where M Na; K (1)

Finally, the carbon bre studied presents a quite low reactivity value, according to its preparation procedure (thermal history). This reactivity value is in the same range as those for the anthracites or for the pyrolysed lignocellulosic materials. 3.4. Adsorption capacity and porosity development; NaOH versus KOH As indicated, Figs. 58 present the N2 adsorption isotherms of the chemically activated carbons prepared in this study from the different selected precursors. A great variability is observed both on the adsorption capacities and on the shape of the isotherms, which emphasises the important role played both by the activating agent and the precursor selected. In this section, the differences observed for the activated carbons prepared by either NaOH or KOH are discussed. Activation by sodium hydroxide (Figs. 5 and 6) allows obtaining ACs with variable porosity development depending on the precursor used. Although N2 adsorption isotherms are mostly type I (corresponding to essentially microporous materials), we can state that most of the activated carbons prepared have a wide microporosity distribution, being the AC prepared from eucalyptus wood (EW) the one that combines the highest porosity together with the widest porosity distribution, comprising an important mesoporosity contribution (as it can be observed from the important slope of its isotherm at relative pressures over 0.2, indicative of the presence of mesoporosity). Activation by KOH (Figs. 7 and 8) also shows the dependence of the porosity development with the precursor used, although, as a tendency, the microporosity distribution is less wide than that obtained with NaOH. Thus, we can observe, for example, small hysteresis cycles and narrower isotherm knees than in the case of NaOH activated carbons. Also, it must be remarked that by KOH activation we were not able to prepare activated carbon samples comparable to that produced by NaOH activation of the eucalyptus wood, combining such high and wide porosity development. Figs. 58 and Tables 4 and 5 showed variable porosity developments for the different chemically activated carbons prepared by physical mixing, with apparent BET surface areas ranging from 630 to 3167 m2 g1 (except for the materials prepared from A1000 which could not be considered as activated). It should be remarked that the obtained porosity results are very reproducible. In addition, these results allow comparing both activating agents in a wide variety of carbon precursors. There seems to be a trend in the porosity distribution which shows narrower microporosity distributions for the ACs prepared by KOH than for those prepared by NaOH. To analyse this trend in more detail, the DFT porosity distributions were obtained for the AC prepared. These results, summarised in Fig. 9 for a selection of materials, show that in the low-ordered materials, such as L, the porosity distribution is wider for NaOH activation in comparison to KOH activation. In medium-ordered materials, such as SB2, NaOH and KOH activated carbons show similar porosity distributions, whereas for highly ordered materials, such as GA, the porosity distribution is wider for the KOH activated carbons.

Previous results [25] showed that the temperature for the beginning of hydrogen evolution during the chemical activation was related to the carbon precursor reactivity. T20 was selected as a parameter related to the reactivity of the precursor. Thus, the lower the temperature for a 20% weight loss, the higher is the reactivity of the precursor in the chemical activation reaction. For this reason, and with the objective of analysing the correlation between these two parameters, the reactivity of all the precursors was determined. Figs. 1 and 2 present the TG curves obtained with the precursors used in this study and Table 3 compiles the temperature for 20% weight loss, which is divided in two parts (left for coals and right for other precursors) and ordered with decreasing the precursors reactivities. In relation to the pristine coals, Table 3 shows the expected trend: (i) the lignite, the lowest rank coal, is the most reactive coal precursor, whereas the anthracites, the highest rank coals, present the lowest reactivities. Thus, the temperature for a 20% weight loss for the anthracites is about two-fold larger than that for the lignite and (ii) Table 3 allows to observe the importance of the pyrolysis; thus, when the coal precursors suffer some pyrolysis (samples CL and A1000) there is a substantial reduction in their reactivity with respect to the pristine coals. Regarding pristine lignocellulosic precursors, Table 3 shows that these materials are in general very reactive (see the almond shell (AS), the coconut shell (CS) and the eucalyptus wood (EW) presenting T20 values similar to the most reactive coal (the lignite)). When these lignocellulosic materials suffer pyrolysis prior to activation, an important decrease in their reactivity to the air reaction is observed, reaching values close to those obtained with the anthracites. This observation was expected according to what occurred with coals pyrolysed at different temperatures [25]. As the pyrolysis temperature increases, the resulting char is less reactive due to both the volatilization of the most reactive carbon atoms and the better structural ordering, easily deduced from XRD.

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3.5. Effect of the precursors reactivity on the adsorption capacities; NaOH versus KOH In this section, the discussion of the effect of the precursors reactivity (summarised in Table 3) is presented. The porosity of the ACs is analysed, rst discussing coal results and afterwards those for the other precursors. 3.5.1. Coals Alkaline hydroxide activation of the pristine coal precursors produces ACs with specic surface areas ranging from 1594 to 2746 m2 g1 (see Table 4). Therefore, this simple physical mixing method is effective for all the coal precursors analysed with both activating agents studied and can be applied to a wide variety of coal precursors different from anthracites. Note that, for a given rank, similar activation performances are observed. However, when different rank coals are compared, differences are noted. This advances that the coal rank has an important effect on the coals activation. Comparing the behaviour of NaOH and KOH for pristine coals (Table 4), it can be seen that for the lower-rank coals (highly reactive precursors according to Table 3), such as L, NaOH produces better porosity development than KOH. For an intermediate coal rank, such as SB1, both activating agents behave similarly, whereas for highly ordered coals such as anthracites (low reactive coals according to Table 3), the inverse behaviour is observed, and KOH produces higher porosity development than NaOH. This behaviour can be attributed to differences in the activation mechanism of both hydroxides, probably diverging in their intercalation behaviour. Thus, KOH activation occurs through K metal formation that may intercalate with the graphene layers, being therefore benecial for the KOH activation the use of precursors with a certain order. However, NaOH activation takes place via a nonintercalation mechanism, which is favoured by some not so organised materials [30]. Regarding pyrolysed coals, Table 3 shows that pyrolysis decreases the reactivity of the precursors and Table 4 shows the effect that pyrolysis prior to the hydroxide activation process has on the porosity. Thus, comparing the pristine lignite (L) with the carbonised one (LC) and the anthracite (A) with the pyrolysed anthracite (A1000) we observe that pyrolysis decreases the porosity development. This decrease, observed for both NaOH and KOH activation agents, is noticeable in the case of the much-better ordered precursor (anthracite, with low reactivity). Interestingly, we also observe for the two pyrolysed coals studied that KOH develops higher porosity than NaOH, even in the case of the carbonised lignite, whereas the opposite happened for the activation of L. This seems to conrm that increasing the structural order of the precursor (by pyrolysis), and thus lowering its reactivity (i.e. CL versus L) makes difcult the activation for both hydroxides, although KOH shows better activation results than NaOH. In other words, the activation process of the precursors that have some structural order, although more difcult, is better for KOH than for NaOH. All these results conrm previous ones recently reported for the activation of nanotubes [30].

Furthermore, the increasing difculty in the activation performance with the increase in the pyrolysis temperature was corroborated with an additional sample, an activated carbon prepared from the anthracite A which suffered pyrolysis up to 1800 8C prior to activation (A1800). No porosity development by chemical activation is possible either for NaOH or for KOH when trying to activate A1800 precursor. 3.5.2. Other precursors In the same way, Table 5 summarises the results for the adsorbents prepared by chemical activation using lignocellulosic precursors. The chemical activation method studied on the pristine materials shows very interesting activation results for the precursors studied, almond shell, coconut shell and eucalyptus wood for both activating agents, with specic surface areas ranging from 1740 to 3167 m2 g1. NaOH activation of lignocellulosic precursors produces activated carbons with an important adsorption capacity joined to a wide porosity development, as it is indicated by the wide knee of the isotherms and the slope at relative pressures over 0.2. However, the results for the eucalyptus wood activated carbon (EW) should be outlined, since it has the highest porosity development among all the materials studied (BET surface area 3167 m2 g1 and total micropore volume of 1.35 cm3 g1) and a wide microporosity distribution, as it is shown by the difference between the nitrogen (total micropore) and carbon dioxide (narrow micropores; <0.7 nm) volumes. The KOH activation for the same precursors shows BET specic surface areas in the range of 17002000 m2 g1. In the activation of almond shell, similar porosities are achieved by NaOH and KOH activation, whereas NaOH shows higher performance than KOH for the eucalyptus wood and the coconut shell. For these precursors, it is seen, more markedly than for coals, that the activation of pristine precursors with KOH develops narrower porosity distributions in the AC than NaOH. Table 3, which compiles the reactivity results for the lignocellulosic precursors, shows that pristine lignocellulosic precursors present very high reactivity, in the range of the lignite coal. For the eucalyptus wood and coconut shell, the activation with NaOH is much more efcient than when using KOH, which is in agreement to what occurs with lignite, with a similar reactivity. Table 3 shows for the carbonised lignocellulosic precursors (CEW, CCS and CAS) the same conclusion as for carbonised coals: pyrolysis previous to the activation over the lignocellulosic precursors causes an important reduction in the reactivity of the precursors. Pyrolysis, as derived from Table 5, causes a strong decrease in the activation of CAS and CCS, in comparison to CEW (note that CEW reactivity is higher than that for CAS and CCS). For the pyrolysed lignocellulosic precursors, as it occurred with the pyrolysed coal precursors, KOH manages to produce activated carbons with higher adsorption capacities, in agreement to what occurs with anthracites, which present reactivities in the same order of magnitude.

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Fig. 10. Effect of the temperature of a pyrolysis step (no previous pyrolysis, pyrolysis at 350 8C and pyrolysis at 850 8C) prior to the activation (at 750 8C) on the porosity (CS-derived precursors).

The importance of the pyrolysis step prior to activation has been analysed over the precursor CS with sodium and potassium hydroxide activation, as it is shown in Fig. 10. A progressive decrease in the porosity is observed when increasing the pyrolysis temperature prior to activation. Focusing on the porosity development of the activated carbon bre, Table 5 shows that the BET specic surface areas, and the total micropore volume (characterised by N2 adsorption at 196 8C), are in the same range when using NaOH or KOH, with a broader porosity distribution in the case of KOH activation. Finally, our results show that there exists some correlation between the reactivity of the precursors and the activation with either NaOH or KOH. Fig. 11 presents a theoretical straight line relating the BET surface area of ACs prepared by NaOH and KOH. The points on the line correspond to precursors with the same specic surface area developed by NaOH and KOH. Points above the line indicate better BET surface area development for KOH and points below mean better porosity development for NaOH. Although the gure shows that the precursors which can be activated with one hydroxide (i.e. NaOH) can also be activated with the other (that is KOH), it highlights the better activation performance with NaOH for low-ordered materials (those with high reactivities according to Table 3, such as the eucalyptus wood, the lignite and subbituminous coals). It also shows the better porosities achieved for KOH when activating more ordered-precursors (those with low reactivity, such as the anthracites and, in general, the pyrolysed precursors). Thus, it can be concluded, as a general trend, that the higher the

reactivity of the precursor, the better activation performance with NaOH in comparison with KOH, whereas those precursors with low reactivity can be more efciently activated by KOH, especially for coals. In summary, it can be stated that: (i) independently of the coal rank used, the coal precursors can be effectively activated by physical mixing of the alkaline hydroxides and the rank of the coal strongly affects the activation process; the higher the rank the higher seems to be the resulting adsorption capacities of the AC (in general the trend for both activating agents is anthracite > subbituminous > lignite), (ii) in the case of the lignocellulosic precursors, these materials can also be effectively activated by alkaline hydroxides, with porosity results comparable or even better to those from coals and (iii) pyrolysis carried out over the precursor prior to activation is detrimental for the activation process, even though this decrease in the activation is higher for the NaOH since the precursor is increasing its structural order. All these observations should call our attention when comparing published results, because the origin and the thermal history of the precursors might be very different. 3.6. Activation yields In this section, the activation yields, that is the ratio of activated carbon obtained to precursor used, for the different ACs are discussed. Tables 4 and 5 compile the yields for the activation with NaOH and KOH for coals and other precursors, respectively. It is important to mention that for a given precursor, the yields are much higher for KOH than for NaOH. A possible explanation for this might be based on the reaction between the hydroxide and the carbonaceous precursor. NaOH seems to have higher reactivity to carbon materials than KOH, producing lower yield than KOH. Consequently, KOH might be more selective in the activation process, causing a more localised reaction with the carbon precursor. Analysing the differences in the yields on the basis of the precursor chosen, the higher the coal rank, the higher the yield, both for NaOH and KOH activation. Interestingly, a high porosity development together with a high yield can be achieved using high rank coals, such as the anthracites, whereas the activation of lignites leads to poorer porosity developments and lower yields. For a given coal, pyrolysis results in a much higher yield, but the porosities achieved from the pristine coals are much higher than for those thermally treated.

Fig. 11. Relationship between the apparent BET surface area of the activated carbons prepared by NaOH and those prepared by KOH.

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In general, for pristine lignocellulosic materials, the obtained yields are very low in the conditions studied, lower than 12 wt% for most of the samples. This is an important drawback for the use of these precursors for the preparation of ACs at large scales. However, when pyrolysis is performed prior to the activation, a strong increase in the yield is observed, which is joined to a decrease in the activation. The high yield obtained in the activation of the commercial precursor C both with NaOH and KOH supports the fact that this material might have suffered some heat-treatment prior to its commercialization. As an example, if the carbonisation yield of sample CAS is taken into account in the calculation of the global yield for NaOH and KOH activation of sample CAS, these values are 20% and 17%, respectively. The comparison of these yields with those of NaOH and KOH activation of AS shows that direct activation leads to lower yield values, 5% and 8%, respectively. Thus, it can be stated that direct activation of a lignocellulosic material is not necessarily an advantage, because the activation yield of the pristine lignocellulosic precursors is much lower than that for the carbonised ones. 4. Conclusions (1) A heat-treatment, in N2 atmosphere, of different precursors and alkaline hydroxide mixtures can be extended to a wide variety of precursors, coals and chars (lignite, bituminous and anthracite), lignocellulosic precursors (pristine and chars; eucalyptus, coconut shells and almond shell) and carbon bre. Variable adsorption capacities and porosity distributions can be achieved depending on the precursor and on the activating agent selected. In general, KOH produces activated carbons with higher yields and with narrower micropore distributions than those prepared by NaOH. (2) The precursors reactivity has an important effect on the activation. In general, the development of porosity for precursors with low structural order (high reactivity) is better with NaOH than KOH, whereas the opposite is observed for the highly ordered ones. (3) The thermal history of the precursor has an important effect on the nal porosity of the ACs. Thus, pyrolysis of the precursor prior to its activation makes the activation process more difcult for both alkaline hydroxides, being higher in the case of KOH. (4) The pyrolysis conditions determine the porosity of the prepared ACs. Thus, low heating rates and moderate heattreatment temperatures, in the range of 750 8C, are desired to prepare high surface area adsorbents. (5) Pyrolysis prior to activation gives higher total yields than direct activation, what is especially interesting for lignocellulosic precursors.

Acknowledgements The authors thank MCYT (PPQ-2003-03884) and European Union Hytrain (MRTN-CT-2004-512443) for nancial support. References
[1] R.C. Bansal, J.B. Donnet, F. Stoeckli, Active Carbon, Marcel Dekker, New York, 1988. [2] T. Kyotani, Carbon alloys, in: E. Yasuda, M. Inagaki, K. Kaneko, M. Endo, A. Oya, Y. Tanabe (Eds.), Novel Concepts to Develop Carbon Science and Technology, Elsevier Science, Oxford, 2003, pp. 109142. [3] A.C. Lua, T. Yang, J. Guo, J. Anal. Appl. Pyrolysis 72 (2004) 279. lu, L. Artok, C [4] C . S entorun-Shalaby, M.G. Uc ak-Astarlog . Sarc, Micropor. Mesopor. Mater. 88 (2006) 126. [5] N.H. Phan, S. Rio, C. Faur, L. Le Coq, P. Le Cloirec, T.H. Nguyen, Carbon 44 (2006) 2569. [6] A.C. Lua, F.Y. Lau, J. Guo, J. Anal. Appl. Pyrolysis 76 (2006) 96. rez-Garc a, A. Mart nez-Alonso, J.M.D. Tasco n, J. Anal. Appl. [7] F. Sua Pyrolysis 63 (2002) 283. o, J. Anal. Appl. [8] P.J.M. Carrott, M.M.L. Ribeiro Carrott, P.A.M. Moura Pyrolysis 75 (2006) 120. [9] E. Gonzalez-Serrano, T. Cordero, J. Rodriguez-Mirasol, L. Cotoruelo, J.J. Rodriguez, Water Res. 38 (2004) 3043. lez, J. Mattusch, A.A. Pela ez-Cid, R. Wennrich, J. [10] M.P. Elizalde-Gonza Anal. Appl. Pyrolysis 78 (2007) 185. [11] T. Otowa, R. Tanibata, I. Masao, Gas Sep. Purif. 7 (1993) 241. [12] J. Hayashi, A.P. Watkinson, K.C. Teo, S. Takemoto, K. Muroyama, Coal Sci. 1 (1995) 1121. n-Go mez, A. Garc a-Garc a, C. Salinas-Mart nez de Lecea, A. [13] M.J. Illa Linares-Solano, Energy Fuels 10 (1996) 1108. [14] A. Ahmadpour, D.D. Do, Carbon 34 (1996) 471. [15] H. Teng, L. Hsu, Ind. Eng. Chem. Res. 38 (1999) 2947. [16] M.J.B. Evans, E. Halliop, J.A.F. MacDonald, Carbon 37 (1999) 269. , M.A. Lillo-Ro denas, D. Cazorla-Amoro s, A. [17] D. Lozano-Castello Linares-Solano, Carbon 39 (2001) 741. denas, D. Lozano-Castello , D. Cazorla-Amoro s, A. [18] M.A. Lillo-Ro Linares-Solano, Carbon 39 (2001) 751. rez, F. Carrasco-Mar n, D. Faire n-Jime nez, C. Moreno[19] R. Ubago-Pe Castilla, Micropor. Mesopor. Mater. 92 (2006) 64. [20] A.A. El-Hendawy, J. Anal. Appl. Pyrolysis 75 (2006) 159. denas, J. Carratala -Abril, D. Cazorla-Amoro s, A. Linares[21] M.A. Lillo-Ro Solano, Fuel Process. Technol. 7778 (2002) 331. -Agullo , B.C. Moore, D. Cazorla-Amoro s, A. Linares-Solano, [22] J.A. Macia Carbon 42 (2004) 1367. [23] Y. Guo, K. Yu, Z. Wang, H. Xu, Carbon 41 (2003) 1645. che , G. [24] A. Perrin, A. Celzard, A. Albiniak, J. Kaczmarczyk, J.F. Mare Furdin, Carbon 42 (2004) 2855. denas, J. Juan-Juan, D. Cazorla-Amoro s, A. Linares[25] M.A. Lillo-Ro Solano, Carbon 42 (2004) 1371. s, J. Alcan iz-Monje, M.A. de la Casa-Lillo, A. Linares[26] D. Cazorla-Amoro Solano, Langmuir 14 (1998) 4589. nez de Lecea, D. iz-Monje, C. Salinas-Mart [27] A. Linares-Solano, J. Alcan s, Tanso 185 (1998) 316. Cazorla-Amoro [28] J. Jagiello, M. Tomes, Carbon 42 (2004) 1227. denas, D. Cazorla-Amoro s, A. Linares-Solano, Carbon 41 [29] M.A. Lillo-Ro (2003) 267. ero, P. Azais, T. Cacciaguerra, D. Cazorla-Amoros, A. [30] E. Raymundo-Pin Linares-Solano, F. Beguin, Carbon 43 (2005) 786.