Colloids and Surfaces A: Physicochem. Eng.

Aspects 232 (2004) 175181

Comparison of the kinetics of methanol adsorption in static and continuous ow conditions on activated carbons with different burn-off degree
G. Finqueneisel , C. Vagner, T. Zimny, J.V. Weber
Laboratoire de Chimie et Applications, EA 3471, Universit de Metz, Rue Victor Demange, Saint-Avold 57500, France Received 2 July 2003; accepted 20 October 2003

Abstract The adsorption of methanol vapour on microporous carbons derived from the carbonization of coconut shell and activated in steam at 1123 K has been studied in a static mode over the relative pressure range 00.96 as well as in continuous ow conditions at temperatures close to ambient. The shape of the isotherm has been discussed and reveals mostly that the mode of acquisition has a negligible effect. In a second step, the kinetics constant rate of adsorption has been determined using a phenomenological mass transfer model (linear driving force). The results demonstrate that the adsorption is favour at low relative pressure (P/P0 < 0.2) under static conditions. This observation is connected to the evolution of the mean free path between the two mode of acquisition. 2003 Elsevier B.V. All rights reserved.
Keywords: Activated carbon; Adsorption; Microporosity

1. Introduction Activated carbons (AC) are used both in gas phase or aqueous phase as a selective adsorbent for industrial separation and purication processes. In gaseous phase adsorption processes, AC are widely used for the removal of volatile organic compounds (VOC) from air streams [1,2]. In this case, adsorption on AC is very complex due to the variety of sites available for adsorption (surface chemistry and especially the presence of oxygenated, nitrogenated groups . . . ) and the heterogeneous nature of the porous structure (volume and size of the pores) [3,4]. These factors are known to signicantly inuence the sorption capacity of carbons and govern their ability to remove and separate different gaseous constituents. Adsorption isotherms and rate constants of adsorption in porous materials are the essential informations for the determination of an adsorbent capacity and calculations for industrial design. If equilibrium information is

obtained relatively easier with well known methods [57] on the contrary only few papers discussing the adsorption of polar substances (such as methanol) on activated carbons in term of kinetic parameters have been published yet [8]. The objectives of this work are: (i) to compare the adsorption capacities of microporous material in static and dynamic conditions; (ii) to determine the kinetic evolution proles in both conditions; (iii) to investigate the effect of burn-off on the kinetic properties of the adsorption. The methanol was chosen principally because it is one of the smallest molecules which exist as a liquid at room temperature. In addition the methanol is a polar molecule but presents also a dispersive character due to his methyl group [9]. The studied sorbents allow us to distinguish the effect of the variation of the degree of burn-off. The results are discussed in terms of the sorption uptake and the adsorption kinetics both in static and dynamic conditions.

Corresponding author. Tel.: +33-3-87-93-9100; fax: +33-3-87-93-9101. E-mail address: gnquen@iut.univ-metz.fr (G. Finqueneisel). 0927-7757/$ see front matter 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.colsurfa.2003.10.025

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Table 1 Elemental analysis of activated carbons Sample NC50 NC60 NC80 NC100 C (%) 89.0 92.3 90.0 92.6 H (%) 0.9 1.2 0.9 1.2 O (%) 4.1 3.2 4.9 2.6 Ash (%) 2.3 2.5 3.1 2.8

2.4. Adsorption studies The adsorption isotherms of methanol vapours were obtained using an intelligent gravimetric analyzer (IGA) supplied by Hiden Analytical Ltd. This apparatus is fully computer controlled and measures gravimetric adsorption and desorption on a microbalance. The IGA instrument allows the adsorption and desorption isotherms and the corresponding kinetics of adsorption or desorption at each step to be determined. The sample temperature was constantly monitored throughout the duration of the experiment, and the variation was found to be 0.05 K. 2.4.1. Static mode The isotherms were obtained by setting pressure intervals relative to the saturation vapour pressure (P/P0 ) at 298 K. Initially, the carbon sample (about 100 mg) was outgassed in situ to a constant weight at a pressure of 106 mbar and at a temperature of 423 K. The liquid used to generate the vapour was degassed fully by repeated evacuation and vapour equilibrium cycles of the liquid supply side of the vapour reservoir. The vapour pressure was gradually increased, over a period of 30 s to prevent disruption of the microbalance, until the desired value was achieved. Pressure transducer with range 010 kPa (accurate to 0.02% of the full scale) was used to monitor the pressure of the vapour in the system. The pressure was maintained constant during relaxation with the help of inlet/outlet control valves with high resolution stepper motors. Pressure steps in the range of P/P0 values 00.95 were used to obtain the isotherm. The mass change as a function of time is analysed in real-time with a computer algorithm in order to predict the equilibrium. After the equilibrium was established, the vapour pressure was increased to the next set pressure value and the subsequent uptake was measured until equilibrium was re-established. The increase in weight due to adsorbate uptake for each pressure step was used to calculate the kinetic parameters for adsorption. The errors in the tted rate constants were typically better than 2% of the value. 2.4.2. Continuous ow conditions About 100 mg of carbon sample was loaded into a bucket made from stainless steel mesh to allow the gas stream to penetrate through the sample. The sample was outgassed at 423 K under vacuum. Then the pressure was gradually increased to atmospheric pressure. After the balance stabilized in the nitrogen ow, the nitrogen ow through the bottom of the sample tube was replaced with adsorptive at different concentration of the same ow rate. In this case, the adsorptive was methanol vapour with nitrogen as the carrier gas. The ow rate was 250 ml min1 . The methanol concentration and the temperature (298 K) were then set to the desired value and the weight uptake was measured with the same sensitive microbalance as a function of time under isothermal conditions until the equilibrium was attained. The same procedure as in static mode was used to monitor the weight

2. Experimental 2.1. Materials used Commercial granular AC: NC50, NC60, NC80 and NC100 (PICA Company, France) differentiated by the degree of burn-off were used. The numbers 50, 60, 80 and 100 reect the increasing burn-off level and correspond to the carbon tetrachloride industrial index. They were obtained by activation of coconut shell in steam at 1123 K. Elemental analysis of the studied activated carbons was determined by the Service Central dAnalyses (CNRS, Vernaison, France) and is reported in Table 1. 2.2. Surface titration The amounts of oxygenated surface groups were determined according to the method of Boehm [4]. One gram of carbon sample was placed in 50 ml of the following 0.05N solutions: sodium hydroxide or hydrochloric acid. The vials were sealed and shaken for 24 h. Then, 5 ml of each ltrate was pipetted and the excess of base or acid was titrated with HCl and NaOH, respectively. The number of acidic and basic sites was calculated from the amount of sodium hydroxide or hydrochloric acid which reacted with the carbon. Due to very low ashes content in all cases (<3.1% in weight), we assume in these work that ashes have no inuence (or few) to the determination (Table 1). 2.3. Surface area measurements The CO2 (298 K) and benzene (298 K) isotherms were measured using a McBain spring apparatus. The benzene and carbon dioxide adsorption isotherms (298 K) were used to calculate the parameters related to submicropores, micropores and mesopores. The values of porosity parameters characterizing these materials have been computed following a procedure described elsewhere [10] The surface area of the mesopores (Smes ) was calculated from their pore size distribution on the basis of the desorption branches of the benzene isotherms, and a slit-like shape of the mesopores has been assumed. The volume of micropores (Vmic ) were also calculated on the basis of benzene isotherms, subtracting the Gurvitch volumes (V0.95 ), taken as the volumes of liquid benzene corresponding to the amounts adsorbed at P/P0 = 0.95, from the previously calculated volumes of mesopores (Vmes ). The surface area was calculated using cross-sectional area of 4.1 1019 m2 for the benzene molecule.

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177

uptake and to calculate the kinetics parameters for methanol adsorption.

Table 2 Structural parameters calculated from benzene sorption Sample Vmic (cm3 /g) 0.384 0.403 0.526 0.585 Vmes (cm3 /g) 0.037 0.053 0.066 0.082 SBET (m2 /g) 961 1005 1326 1493 Smes (m2 /g) 19 29 35 48

3. Results and discussion 3.1. Characteristics of the samples AC used in this study differ signicantly in their pore structure, calculated from benzene isotherms. Table 2 shows that our samples are microporous carbons with specic surface area close to 1500 m2 /g for NC100. The acidic and basic oxygenated surface groups were determined using Boehm titration. The results obtained are very similar for all studied samples whatever the burn-off degree (Table 3). The samples have primarily basic groups. The number of acidic groups was very low (<0.08 meq g1 ). This observation can logically be attributed to the production process: the lower the temperature of carbonisation the higher the amounts of acidic oxygenated surface groups and the higher the temperature the higher the amounts of basic oxygenated groups [11]. To resume, the studied AC have similar surface chemistry, but different microporous capacities. 3.2. Adsorption of methanol vapour in static mode The isotherms corresponding to the exposition of NCx carbons to the methanol vapour are shown in Fig. 1. In general terms, it is apparent that isotherms have a similar shape for all NCx carbons and are type I (BDDT classication). This is consistent with the microporosity being the
18

NC50 NC60 NC80 NC100

Table 3 Boehm titration results Sample NC50 NC60 NC80 NC100 Basic groups (mequiv/g) 0.46 0.49 0.51 0.50 Acidic groups (mequiv/g) 0.08 0.05 0.08 0.06

major part of the porous structure with a wide micropore size distribution (as denoted by the opening of the knee in the isotherm) with a small contribution from larger porosity (as denoted by the almost at plateau). As expected, the amount adsorbed at saturation increases with the degree of burn-off. The highest uptake of methanol observed for the NC100 sample is the result of its highest micropore volume. Nevertheless, a crossover of the isotherms at very low relative pressure (around 0.08) is observed. Below this value the amount adsorbed by the NC100 carbon is smaller than the other samples. The dispersive interactions between the methanol molecule (methyl group) and the carbon pore walls could explain the behaviour before the crossover (at low relative pressure). This is conrmed by Inverse Gas

15

-1

) Molar Uptake (mmol . g

12 9 6 3 0 0.0 0.1 0.2 0.3 0.4 0.5 0.6

P/P 0
Fig. 1. Methanol adsorption isotherms in static mode for series of carbons NCx (NC50 (); NC60 (); NC80 (); and NC100 ()).

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18

Am ount uptake (mm ol.g )

-1

15

12

0 0 20 40 60 80 100

% m ethanol concentration
Fig. 2. Methanol adsorption isotherms in ow continuous conditions for series of carbons NCx (NC50 (); NC60 (); NC80 (); and NC100 ().

Chromatography at innite dilution. The procedure and results were discussed elsewhere [12]. This method allows the determination of the dispersive component of the surface d ). With the studied AC, the free energy of adsorption (s larger the burn-off, the larger the pores and the weaker the d . This parameter indicates the most energetic sites and the s carbon with the lowest burn-off has the highest dispersive component. That means, at low burn-off degree the micropores are more energetic, and at high burn-off degree the consumption of carbon allows the enlargement of the pores size leading to a decrease of their dispersive component (NC50: d = 495 15 mJ/m2 and NC100: d = 460 15 mJ/m2 ). s s 3.3. Adsorption of methanol vapour in dynamic ow conditions The isotherms of methanol adsorption on NCx carbons are presented in Fig. 2. The isotherms are type I, which is representative of the microporous samples. Their general shape is similar to the isotherms obtained in static mode. It is noteworthy that a crossover occurs at relative concentration around 7% which can be correlated to a relative pressure equal at 0.07. After this point, the amount adsorbed increases with the degree of burn-off. In both cases, the total pore volumes obtained from extrapolation of the methanol adsorption plateau at high

relative pressure or concentration are given in Table 4. The volume was calculated using density of 0.7870 g cm3 for the methanol at 298 K. The micropores volume obtained for adsorption of benzene on NCx coincides with the pore volumes obtained from methanol adsorption under owing conditions. It is noteworthy that it is different under static conditions: the adsorbed volumes of methanol are higher than adsorbed volumes of benzene. This particular point is not explained yet and need some complementaries analyses. The comparison between the methanol isotherms for adsorption of vapours in both static and owing nitrogen environment showed that: at low relative pressure (P/P0 < 0.2) or concentration (<20%), the amounts of methanol uptake are the same; near the saturation, except for NC50 sample where the results are similar in both cases, the amount adsorbed in static mode is higher than in dynamic mode. For example, the NC100 sample adsorbs 16.1 mmol g1 at saturation in static mode and 14.1 mmol g1 in continuous ow conditions. The nitrogen used as carrier gas had probably an effect on the micropores lling. This is consistent with a competition of adsorption between nitrogen used as carrier gas and methanol under our experimental conditions. To check this point, helium was used as carrier gas leading to the

Table 4 Volumes of methanol adsorbed at saturation in static and dynamic ow conditions Sample C6 H6 adsorption Vmic NC50 NC60 NC80 NC100 0.384 0.403 0.526 0.585 (cm3 g1 ) Static mode ns (mmol g1 ) Vs (cm3 g1 ) Flowing mode ns (mmol g1 ) 9.3 10.2 12.8 14.1 Vs (cm3 g1 ) 0.379 0.415 0.521 0.574

9.0 11.6 13.7 16.1

0.366 0.472 0.558 0.655

G. Finqueneisel et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 232 (2004) 175181
9.0x10 8.0x10 7.0x10
-3

179

-3

-3

rate constant (s )

-1

6.0x10 5.0x10 4.0x10 3.0x10 2.0x10 1.0x10

-3

-3

-3

-3

-3

-3

0.0 0.00 0.05 0.10 0.15 0.20

P / P0
Fig. 3. Kinetic rate constants for methanol vapour adsorption on carbons NCx (NC50 (); NC60 (); NC80 (); and NC100 ()).

superimposition of the isotherm. Furthermore this effect does not vary with the dimension of the gas molecule. 3.4. Kinetics of methanol adsorption in static mode The transport of vapours into an activated carbon is a complex process. In our case, our objective was to follow the kinetic of adsorption versus the relative methanol pressure. For this reason we used the phenomenological model widely used in the literature [13,14]: Mt = 1 ekt (1) Me where Mt is the uptake at time t, Me the equilibrium uptake, and k the rate constant. The reason why this equation can be used to model adsorption was discussed elsewhere [15]. Hence for a pressure or a concentration step (isobaric condition) a plot of ln (1Mt /Me ) versus time will be linear with a gradient equal to the rate constant. The graph is close to linearity for >90% of the total uptake for each specic pressure step and for all the studied samples. The results obtained for NCx carbons show a similar trend of rate constant with increasing burn-off (Fig. 3): initial fast decrease and then a slow increase of the rate constant. The relative pressure at the minimum increases when the activation time of the carbons increases. For carbon NC100, a minimum rate constant was observed at P/P0 = 0.1. This corresponds to the part of the isotherm where the adsorption capacity is increasing markedly with increasing relative pressure. After P/P0 = 0.1, the constant k increases slowly with the surface coverage. Some authors studied the kinetics of methanol adsorption on active carbon under static vapour conditions and showed that the variation in rate constant with surface coverage for different adsorptives (alcohols, alkanes . . . ) covers a wide range of behaviour [16]. In our case, it seems that the evolution of the rate constant at very low relative pressure (<0.02)

is different because this is not a peak, only a decrease of the rate constant is observed. It is reasonable to conclude that barriers develop during the adsorption process that cause a decrease in rate constant. It can be assumed that the rate of adsorption is connected with the diffusion phenomena [17,18]. Consequently, it seems that the evolution of rate constant versus the methanol mass uptake can be considered. The Fig. 4 shows the evolution of the rate constants k with the variation of methanol amount adsorbed on studied AC. In this case, the same pressure step has been considered: P = 2%. This condition was used over the range of relative pressure 00.15. The mass uptake between two pressure steps is called hereafter m. For the NC-carbons, the curves can be divided in two domains. In the rst domain, corresponding to the highest uptake and to the lowest relative pressure (rst points of the isotherms) the rate constant k decreases strongly at m quasi-constant. Logically this domain is shifted with increasing burn-off ( m = 17.5 mg/g for NC50 and 12.2 mg/g for NC100). In the second domain, another situation is observed. The rate constant k is almost constant and m values decrease with the relative pressure. This gure shows the mass transport problems for NC-carbons which occur in this relative pressure domain. Considering the proles of the kinetic constant, the effect of heat of adsorption can not be avoided especially for the rst relative pressure. Nevertheless, the following arguments have to be considered to neglect it: the kinetic of adsorption is relatively slow; the isosteric heat of adsorption was obtained with four different temperatures (288, 293, 298 and 303 K) and the ClausiusClapeyron equation [19]. In our case, the isosteric heat of adsorption has low values (from 20 to 35 kJ mol1 ) in the rst domain of adsorption (high mass uptake). The same values were obtained by Salame and Bandosz [20];

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domain 1 8.0x10 7.0x10 6.0x10 5.0x10 4.0x10 3.0x10 2.0x10 1.0x10
-3

-3

-3

rate constant (s )

-1

-3

-3

-3

-3

-3

domain 2 0 2 4 6 8 10 12
-1

14

16

18

20

weight (mg.g
Fig. 4. Variation of rate constant vs. (); NC80 (); and NC100 ()).

m for NCx carbons (the lines represent the general trend of the curves for all the samples). (NC50 (); NC60

the kinetic constant values, and more generally the kinetic constants proles are similar if the pressure drop increases. The increasing burn-off level allows an initial decrease of the m value due to the disappearing of the most energetic micropores. But whatever the burn-off, the proles of rate constants evolutions are similar proving that the mechanism of pores lling is the same. So the microtexture of the pores (shape and size) but also the precursor and fabrication process seem to have a prime importance on the kinetic of adsorption [21].

3.5. Kinetics of methanol adsorption in continuous ow conditions In our case, the kinetics of methanol vapour adsorption in continuous ow conditions follow also the phenomenological mass transfer model. Fig. 5 shows the kinetic data for methanol vapour obtained at 298 K for a range of relative concentration obtained using the continuous ow apparatus. For NCx carbons, the rate constant increases with the relative concentration of methanol. Moreover, the rate constant decreases with the degree of burn-off.

1.0x10

-2

8.0x10

-3

rate constant (s )

-1

6.0x10

-3

4.0x10

-3

2.0x10

-3

0.0 0 10 20 30 40

relative concentration (% )
Fig. 5. Kinetic rate constants for methanol vapour adsorption on carbons NCx in continuous ow conditions (NC50 (); NC60 (); NC80 (); and NC100 ()).

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These results allow a comparison between the static methanol vapour atmosphere and dynamic ow methanol vapour/nitrogen systems. The same trend is observed but in continuous ow conditions the rate constant does not reach a minimum at low concentration. In our experimental conditions, it is difcult to obtain some points at relative concentration less than 5%. The most important observation is that, at low pressure (P/P0 < 0.1) or concentration (<10%), the values of the rate constant for the static system are higher than the rate constant for the dynamic ow system. The presence of nitrogen slowed the kinetics for methanol adsorption markedly: divided by 3 at low concentration. Then the gas phase diffusion is inuencing the adsorption kinetics. The methanol isotherm is type I in the IUPAC classication and then the major part of the adsorption uptake occurs at low relative pressure (P/P0 < 0.2), which corresponds to a pressure of around 30 mbar at 298 K. In this domain the gas phase and the Knudsen diffusion will be dominates by nitrogen, the carrier gas present in large quantities in the gas phase at this concentration. The Knudsen diffusion occurs when the molecules in the gas phase collide with the pore walls. This is predominant when the mean free path of the molecules is a lot larger than the diameter of the pores. In our case, the mean free path in static vapour at 30 mbar is around 10 m compared with 0.3 m at atmospheric pressure in owing vapour. Then the pore size where Knudsen diffusion occurs is different and inuences the kinetics of adsorption. The same conclusion was obtained by Fletcher et al. though the adsorption of methanol, water and alkanes vapours on active carbon [22].

a carrier gas may have a market effect on the adsorption kinetics at low pressure (P/P0 < 0.2): the kinetic constants are highest in static mode. The difference in the mean free path, resulting from the difference in total pressure under static and owing vapour conditions is the major factor inuencing diffusion in the gas phase and in the pores. Above P/P0 > 0.2, the rate constants in static vapour and owing nitrogen are virtually identical and this is attributed to rate determining diffusion into the porous structure.

Acknowledgements This research work is supported by CNRS, in the frame of the Jumelage Matriaux carbons et catalytiques pour lenvironnement. References
[1] M.P. Cal, M.J. Rood, S.M. Larson, Gas separation purication 10 (2) (1996) 117121. [2] K.L. Foster, R.G. Fuerman, J. Economy, S.M. Larson, M.J. Rood, Chem. Mater. 4 (1992) 10681073. [3] C. Yu-Chun, C. Pen-Chi, H. Chin-Pao, Carbon 39 (2001) 523. [4] H.P. Boehm, Carbon 32 (5) (1994) 759. [5] H. Marsh, Carbon 25 (1) (1987) 4958. [6] N. Wang, M. Sasaki, T. Yoshida, T. Kotanigawa, Energy Fuels 11 (1997) 12931298. [7] D.D. Do, H.D. Do, Langmuir 18 (2002) 9399. [8] H.K. Chagger, F.E. Ndaji, M.L. Sykes, K.M. Thomas, Carbon 33 (10) (1995) 14051411. [9] P.J.M. Carrott, M.M.L. Ribeiro Carrott, I.P.P. Cansado, Carbon 39 (2001) 193200. [10] T. Siemieniewska, K. Tomkow, J. Kaczmarczyk, A. Albiniak, Y. Grillet, M. Francois, Energy Fuels 4 (1990) 6170. [11] S.S. Barton, M.J.B. Evans, E. Halliop, J.A.F. MacDonald, Carbon 35 (9) (1997) 13611366. [12] L. Cossarutto, C. Vagner, G. Finqueneisel, J.V. Weber, T. Zimny, Appl. Surf. Sci. 177 (2001) 207211. [13] C.R. Reid, K.M. Thomas, Langmuir 15 (1999) 32063218. [14] I.P. Okoye, M. Benham, K.M. Thomas, Langmuir 13 (1997) 4054 4059. [15] S. Sircar, J.R. Hufton, Adsorption 6 (2000) 137147. [16] A.J. Fletcher, K.M. Thomas, Langmuir 16 (2000) 62536266. [17] J. Mugge, H. Bosch, T. Reith, Chem. Eng. Sci. 56 (2001) 53515360. [18] D.D. Do, H.D. Do, I. Prasetyo, Chem. Eng. Sci. 55 (2000) 1717 1727. [19] H. Pan, J.A. Ritter, P.B. Balbuena, Langmuir 14 (1998) 63236327. [20] I.I. Salame, T.J. Bandosz, Langmuir 16 (2000) 54355440. [21] C. Vagner, G. Finqueneisel, T. Zimny, J.V. Weber, New Carbon Mater. 18 (2) (2003) 133. [22] A.J. Fletcher, M.J. Benham, K.M. Thomas, J. Phys. Chem. B 106 (2002) 74747482.

4. Conclusion This paper deals with the study of methanol adsorption on activated carbons having different burn-off level in both static and dynamic conditions. In both cases, the shape of isotherms is similar and the amount adsorbed near saturation increases with the microporous volume of the samples connected with the burn-off degree. We clearly observe that the adsorption under owing vapours in nitrogen as carrier gas showed that the presence of nitrogen decreases the capacities of adsorption due probably to a small quantity of nitrogen adsorbed in the micropores. Comparisons between adsorption kinetics under static and owing conditions show that the inuence of the burn-off degree is small. Under owing conditions, the presence of