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Pergamon 000%6223(95)00090-9

Carbon Vol. 33, No. 10, pp. 1417-1423,1995 Copyright 0 1995 ElsevierScienceLtd

Printed in Great Britain.All rights reserved OLW8-6223/95 $9.50 + 0.00

THERMAL REGENERATION OF AN ACTIVATED CARBON EXHAUSTED WITH DIFFERENT SUBSTITUTED PHENOLS


C. MORENO-CASTILLA, I* J . RIVERA-UTRILLA, J. P. JOLY,~ M. V. LOPEZ-RAM~N, M. A. FERRO-GARCIA and F. CARRASCO-MAR~N
Departamento de Quimica Inorginica, Facultad de Ciencias, Universidad de Granada, 18071 Granada, Spain Laboratoire dApplication de la Chimie g lEnvironnement, CNRS, Universitk Lyon 1, ESCIL, 69622 Villeurbanne cedex, France
(Received 22 January 1995; accepted in revised form 1 May 1995)

Abstract-The thermal desorption process of phenol, m-aminophenol, p-cresol and p-nitrophenol from an activated carbon has been studied. For this purpose, the activated carbon-phenolic compound system was heated to 1100 K in a He flow following determination of weight loss and the evolution of light gases by a thermobalance and by mass spectrometry, respectively. Results showed that during the heat treatment, part of the phenol evolved from the activated carbon and was deposited at the outlet of the reactor and part underwent degradation reactions to light gases and to a residue that remained on the surface of the activated carbon. Finally, the variation of the adsorption capacity of the activated carbon after several adsorption-regeneration cycles has also been studied. Key Words-Regeneration, activated carbons, substituted phenols.

1. INTRODUCTION Activated carbons are widely used to remove organic pollutants from water but, depending on their adsorption capacity, they become saturated after some time. If these activated carbons need to be reused as adsorbents, they therefore have to be regenerated. One of the cheapest and most versatile methods of regenerating activated carbons is by thermal treatment in a given atmosphere[ 1,2]. In previous papers, activated carbons from a Spanish bituminous coal were found to have both high surface area and appropriate porosity[3] to extensively adsorb phenolic compounds such as: phenol, p-cresol, m-aminophenol, chlorophenols and p-nitrophenol[4]. The thermal regeneration process of an activated carbon from almond shells saturated with both orthochlorophenol and metachlorophenol has been studied previously [ 5,6]. The physisorbed fraction was found to be eliminated as chlorophenol molecules and/or heavy products of their degradation. The chemisorbed fraction, however, underwent degradation reactions giving light products such as H,, H,O, CO and CO,, with the oxygen surface groups of the activated carbon playing an important role in the production of these gases, and also yielded a residue or polymer that remained on the surface of the activated carbon. The aim of this paper is to gain more insight into the thermal desorption processes of phenols from activated carbons. Thus, in the present study four phenolic compounds (phenol, p-cresol, m-aminophenol and p-nitrophenol) have been chosen, which *To whom correspondence
CM

together with the previously published work carried out on chlorophenols[ 5-71, will enable us to develop a more general picture on the thermal desorption processes of the phenolic compounds, which are of great importance in the regeneration processes of exhausted activated carbons.

2. EXPERIMENTAL The activated carbon used in this study (APlO) was obtained by pyrolysis in N2 and steam activation of a Spanish bituminous coal. Details of the method of preparation and characterization of this activated carbon and the values of its more important textural and chemical parameters have been reported in previous papers[3,8,9]. Some of these are as follows: surface area=828 mz g- (determined from the N, adsorption isotherm by applying the BET method); pore volume accessible to water =0.52 cm3 g-l; and pH = 10.0. The activated carbon was independently saturated with phenol (P), p-cresol (PC), m-aminophenol (MAP) and p-nitrophenol (PNP) as follows: 0.5 g of activated carbon were added to 100 cm3 of different phenolic solutions (1 g 1-l). The suspensions were thermostatized at 298 K and mechanically shaken for 3 days. They were then filtered out and the spent activated carbon was dried in an oven at 393 K for 2 hours, after which the cooled activated carbon was carefully weighed. Table 1 summarizes the amounts of phenolic compounds adsorbed on the activated carbon and determined by spectrophotometry (X,), the amounts remaining on the activated carbon after drying in the oven (X) and the percentages of phenolic

should be addressed.

33-10-c

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Table 1. Adsorption capacity, compound left on the carbon

C. MORENO-CASTILLA et al. X,, of the activated carbon APlO. Amount of phenolic after drying, X. Amounts of oxygen contained in the

adsorbed phenol, X,, and contained in the light gases, X,, detected by TPD-MS X, Sample AP-10 AP- lo-phenol AP-lo-m-aminophenol AP-lo-p-cresol AP-lo-p-nitrophenol X %W 18.6 11.8 13.6 8.2 X0 X0 A(X,-X,) 12 21 15 8

mg phenol g- C 167 178 209 196 136 157 181 180

mg 0 g- C 23 23 27 62 9 35 44 42 70

compounds released from the activated carbon during the oven drying process (%W). Thermal regeneration of the spent activated carbon samples was followed by both TGA and TPD-MS techniques. TGA experiments were carried out with a CI Electronics thermobalance (model MK3). About 10 mg of sample was heated in an ultrapure, dry He flow (200 cm3 mini) at a heating rate of 20 K min- up to 1100 K. The TPD-MS experiments were carried out by placing about 200 mg of sample in a dynamic quartz reactor equipped with a short response time capillary thermocouple in its center. The sample was heated in a He flow (60cm3 min-) at a heating rate of 20 K min- up to 1100 K. On-line gas analysis was followed with a quadrupole mass spectrometer (MS) with a capillary introduction system heated at 373 K. The MS apparatus was able to detect only light gases. The apparatus and data processing have been described in detail in previous publications [ 10-121.

300

500

700 TIKI

900

1100

Fig. 2. TPD-MS He flow. Heating

pattern of the APlO-phenol system in a rate: 20 K mini. W H,; 0 H,O; + CO; 0 co,.

3. RESULTS

300

400

500

600

700

800

900

1000

1100

T(K) Fig. 3. TPD-MS pattern of the APlO-m-aminophenol system in a He flow. Heating rate: 20 K min-. n H,; 0 H,O; + CO; 0 CO,; 0 N,; 0 NH,.

The data in Table 1 show that during the oven drying process of the different APlO-phenolic compound systems, a fraction of the adsorbed phenol was released from the activated carbon, caused by the drag of the adsorbate molecules by the water evaporation. The weight loss percentage (%W) is lower for p-nitrophenol because of its higher interaction with the surface of the activated carbon[4]. The TPD-MS spectrum of activated carbon APlO is depicted in Fig. 1, and those corresponding to the four APlO-phenolic compound systems in Figs 2-5. Table 2 summarizes the total amounts of light gases

1
S
Lc

0,s

0.4 0
300 400 500 600 700 800 900 1000 1100

T (K) Fig. 4. TPD-MS He flow. Heating pattern of the APlO-p-cresol system in a rate: 20 K min-. H H,; 0 H,O; l CO; 0 COz; 0 N,; 0 CH,.

ci > 2 0.25 t k.

0 300

500

700 T(K)

900

1100

Fig. 1. TPD-MS pattern of activated carbon how. Heating rate: 20K min-. n H,; 0 0 co,.

APlO in a He H,O; l CO;

detected by MS in the TPD experiments whose desorption profiles are shown in the above figures. Table 1 also includes the amounts of oxygen corresponding to both the adsorbed phenol (X6) determined from X and the degradation compounds detected by TPD-MS and given in Table 2 (X,). In order to evaluate the total amount of the different phenols eliminated during the thermal regen-

Thermal regeneration of an activated carbon Table2. Amounts (pmol g-) of light compounds evolved from APlO and APlO-phenolic compound systems heated up to 1100 K in a He flow Sample AP-10 AP-lo-phenol AP-lo-m-aminophenol AP-lo-p-cresol AP-lo-p-nitrophenol H2 14 28.5 488 658 253 H,O 410 710 1098 1003 1563 CO 94 1188 1002 1137 1397 CO* 39 154 330 243 723
0.3

1419

CH, 223 -

NH, 201 -

NO 110

N, 299 455

o-0
4 $3 s =2 % I 0 300 400 SO0 600 700 T(K) 800 900 IOW 1100 0 300 SO0 700 T(K) 900 1100
3

a
0

r^ * 0.2 a 5 5 5 0.1

,.

(p&&q_,

Fig. 5. TPD-MS pattern of the APlO-p-nitrophenol system in a He flow. Heating rate: 20K min-. n H,; 0 H,O; + CO; 0 CO,; 0 N,; A NO. eration of the samples, these regeneration processes were followed in a thermobalance determining the total weight loss as a function of temperature. Figures 6-9 show both the DTG thermograms and the overall mass calculated from MS analysis for each APlO-phenolic compound system. Whereas DTG data inform about the total weight loss per gram of sample, the TPD-MS data correspond only to the weight of the light compounds detected by MS; thus, comparison of both thermograms for the same sample

Fig. 8. DTG thermogram (--- ) and overall mass of light gases calculated from TPD-MS (-) for the APlO-p-cresol system.

300

400

500

600

700 T(K)

800

900

1000

1100

Fig. 9. DTG thermogram (---) and overall mass of light gases calculated from TPD-MS (-) for the APlOp-nitrophenol system.

is beneficial because it simultaneously informs us about the total amount desorbed and the fraction converted to light products.
300 4m so0 600 700 T(K) 800 900 1000 1100

4. DISCUSSION The TPD-MS results for activated carbon APlO, (Fig. 1 and Table 2) are typical of carbonous materials with a low oxygen content. The amount of CO desorbed is more than the double that corresponding to COz. According to the basic nature of this carbon[4], this CO might come from surface groups such as pyrone, quinone and carbony1[3,13]. The amount of oxygen in the light products detected by TPD-MS, up to 1100 K for APlO (9 mg g- of C), is much lower than its oxygen content (8%), determined by elemental analysis.

Fig. 6. DTG thermogram (--- ) and overall mass of light gases calculated from TPD-MS (-) for the APlO-phenol system.

300

400

SO0

600

700 T(K)

BOO

900

1000

1100

4.1 API O-phenol system


During thermal treatment of the APlO-phenol system up to 1100 K the following are observed (Fig. 6):

Fig. 7. DTG thermogram (--- ) and overall mass of light gases calculated from TPD-MS (-) for the APlO-maminophenol system.

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C. MOKENO-CASTILL.Aet 01.

(i) Between 300 and 425 K, 6% of the phenol (P)


adsorbed is released and light gases are not detected by MS. This P will come from the physisorbed fraction and is deposited at the outlet of the reactor either as P or as a heavy compound[5]. (ii) Between 425 and 925 K, the profiles of both DTG and MS curves are similar in shape with two maximum peaks at about 550 and 675 K. respectively, although the amplitude of the DTG curve is greater than that of MS. These results indicate that the P desorbed in this region corresponds to that chemisorbed[ 51 and is evolved as light gases detected by MS and as heavy products detected only by TG and deposited at the outlet of the reactor. The similarity of both the DTG and MS profiles suggests that light gases and heavy products proceed from parallel processes. (iii) Above 925 K, both DTG and MS profiles are coincident. This shows that only the light gases detected by MS are released in this region; these gases will also come from the chemisorbed fraction. The total weight loss of this system detected by TG by heating to 1100 K was 71% of the adsorbed phenol (X). This means that there is a residue on the surface of the activated carbon that proceeds from the chemisorbed fraction and that should be rich in carbon[ 141. The amount of light gases detected by MS was only 48%. The difference in weight loss between TG and MS (33%) is due to P and heavy compounds, coming from both the physisorbed and chemisorbed fractions evolved from the activated carbon and deposited at the outlet of the reactor. Figure 2 and Table 2 show the TPD profiles of the light gases and their amounts, respectively. As expected from thermal degradation of P, the main degradation compounds are CO and H,O. The oxygen surface groups of the activated carbon should participate in some of the phenol degradation processes since the total amount of oxygen corresponding to the degradation compounds (35 mg g- of carbon) is greater than that corresponding to the adsorbed of the P(23mg g-r of C) (Table 1). Participation oxygen surface groups of the activated carbons in the thermal regeneration process is expected because the adsorption of phenolic compounds on the surface of the activated carbons implies a donor-acceptor complex mechanism involving carbonyl oxygens of the carbon surface acting as electron donors and the aromatic ring of the adsorbate acting as the acceptor [ 151. Therefore, as reported previously [ 51, these oxygen surface groups play an important role in the thermal regeneration of the activated carbons by cracking the adsorbate molecules, 4.2 API&m-aminophenol During the thermal treatment of the APlO-maminophenol system up to 1100 K the following are observed (Fig. 7):

(i) Between 300 and 450 K, the weight loss detected


by DTG is 31% of the initial amount adsorbed (X) and it comes from both the physisorbed fraction of MAP and essentially physisorbed water, although the contribution of the latter is negligible, (see Fig. 3). This MAP is not detected by MS, as in the above system, and is deposited at the outlet of the reactor. (ii) Above 475 K, both the DTG and MS curves are more or less coincident, implying that all MAP released is degraded to light gases detected by MS (Hz, H,O, CO, CO,. NH, and N, (see Fig. 3 and Table 2). These light gases come from the chemisorbed MAP fraction. and, as in the above system. the oxygen surface groups of the activated carbon participate in the degradation reactions (see the value of A (X0-X,) in Table 1). At the end of the experiments, the total mass eliminated with regard to the initial amount of MAP adsorbed (X) was 83% (detected by TG), which indicates that a carbonaceous residue is also left on the surface of the activated carbon proceeding from the chemisorbed fraction. The total mass of light gases detected by MS was 48% of the initial MAP adsorbed. In this case the difference between the weight loss obtained by TG and MS. 350/o, should essentially correspond to the physisorbed fraction evolved from the activated carbon between 300 and 450 K and deposited at the outlet of the reactor, because as shown before no heavy products were released above 450 K. Therefore, in this system, in contrast to the above, the chemisorbed fraction evolved only as light gases.

4.3 API O-p-crrsol


Regarding the APlO-p-cresol system, the following points can be deduced from Fig. 8: 380 K. only PC is released (which amounts to 1.5% of the initial PC adsorbed, X) without any defined peak in the DTG curve. This behaviour is different to that found in the above systems, and implies either that there is a small amount of PC physisorbed or that during the heat treatment a large amount of physisorbed PC is transformed to chemisorbed PC. This latter transformation has been observed before in other activated carbonphenohc compound systemsC2.71. The amounts of both PC and MAP physisorbed by the activated carbon should be similar because, as shown recently[4], the interaction of both molecules with the surface of the carbon is also similar due to the fact that both substituents of the phenolic compound (methyl and amino) are electron-donating to the aromatic ring. Therefore, from the above two assumptions, the transformation from physisorbed to chemisorbed PC should hold. (ii) Between 380 and 925 K, the DTG and MS

(i) Below

Thermal regeneration of an activated carbon profiles are similar in shape, but the amplitude of the DTG signal is greater than that of the MS. This means that in this range of temperature the chemisorbed fraction of PC evolved as light gases and heavy compounds, which were detected and not detected by MS, respectively. This behaviour is also analogous to that of the APlO-phenol system. (iii) Surprisingly, the MS signal is higher in amplitude than that of DTG above 925 K. The explanation of this apparent anomaly is to be found in the different experimental conditions in both techniques. Thus, the mass of the sample is about 20 times greater and the inert gas flow -about 3 times lower in MS than in TG. The pressure of PC is therefore about 60 times higher in MS than in TG experiments. Re-adsorption of physisorbed PC should thus be favoured in the case of MS experiments. It is noteworthy that re-adsorption of physisorbed chlorophenols has been reported recently [ 71. In turn, re-adsorption of physisorbed PC favours its transformation into a chemisorbed form, which further transforms and decomposes during heat treatment. In the case of MS experiments, a greater amount of chemisorbed PC is formed around 380 K and consequently more degradation products are expected. In the present case, most of these products should be light gases evolved above 925 K. This apparent anomaly thus corroborates the assumption that physisorbed PC is transformed into the chemisorbed species. More information about this transformation can be gained from the results of TPD-MS (Fig. 4). A characteristic of the MS spectrum of PC is the evolvement of CO at low temperatures, which can only proceed from chemisorbed species. Thus, CO is evolved from PC at 150 K lower than from MAP (Fig. 3). The beginning of CO desorption is also higher for P (Fig. 2). Besides, the amount of CO desorbed up to 700 K, is around 1.4 times greater for PC than for MAP. This CO desorbs into two peaks at 420 and 560 K, which are not found in the MAP spectrum. This suggests that low temperature CO desorption is due to the methyl group of PC. The proposed mechanism for the transformation of physisorbed PC into chemisorbed PC in the first step of the heat treatment is as follows: Gas phase Sorbed Ph-CH,

1421

hydrogens, which are themselves relatively mobile. As re-adsorption of PC is possible, a greater pressure of p-cresol in the gas phase results in a more intense re-adsorption and consequently favours the formation of the chemisorbed form from the physisorbed one. Reaction of some of the benzylic radicals with oxygen surface groups might be the reason for the low temperature CO evolution. Another interesting feature in Fig. 4 is the evolution of methane between 750 and 1100 K. This methane should originate from a part of PC that did not undergo the benzylic abstraction described above and is probably due to its thermal demethylation. Desorbed methane amounts to 223 pmol g- of carbon, a very small quantity compared to the amount of methyl in the adsorbed PC (X), i.e. 1680 pmol g-. This result agrees with the assumption that a part of PC undergoes abstraction of benzylic hydrogen at the beginning of the heat treatment. The total weight loss up to 1100 K of the APlOp-cresol system determined by TG was 46% of the total amount of PC adsorbed, indicating that the amount of residue left on the surface of the activated carbon is the greatest of all the systems studied. This result can be also explained by the mechanism proposed in the scheme above [ 11. Thus, the benzylic radicals formed could undergo reactions such as the formation of polymers on the surface of the activated carbon and/or its stabilization through the reaction with dangling carbon atoms of the activated carbon microstructure, giving rise to stable C-C bonds. The total weight loss due to light gases was 29%; 17% (46- 29) of the total weight loss detected by TG, therefore, corresponds to heavy compounds that are evolved from the activated carbon and deposited at the outlet of the reactor. 4.4 API 0-p-nitrophenol During the heat treatment of the APlO-pnitrophenol system up to 1100 K the following are observed (Fig. 9): p-nitrophenol is desorbed and there is no appreciable evolution of light gases from the system. As in other systems, the PNP desorbed is deposited at the outlet of the reactor either unchanged or as a heavy compound. The amount desorbed up to this temperature is 10% of the total amount adsorbed. (ii) Between 450 and 750 K, the DTG and MS profiles have the same shape, with two peaks appearing at around 550 and 700 K. The peak at 550 K obtained from the DTG experiment presents a higher intensity than that obtained from the MS experiment, indicating that both light gases and heavy compounds are released from the system at this temperature. These products will stem from the chemisorbed fraction of PNP. The amplitude of the peak at 550 K is the highest found of all the systems studied.

(i) Below 450 K, the physisorbed

11
phase Ph-CH,
physisorbed

--+

-H'

Ph-CH,chemisarbed

reaction with oxygen surface groups reaction with dangling C atoms polymerization

(1)

Physisorbed PC desorbs and at the same time reacts on the surface of the carbon to produce a chemisorbed species through the abstraction of one of its benzylic

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C. MORENO-CASTILLA

etal. evolved in this region, CO is the main product, with negligible amounts of water evolved.

On the contrary, the peak at 700 K is smaller in amplitude and that obtained from DTG is fairly coincident to that from MS. The profiles of the light gases evolved in this temperature range are shown in Fig. 5. The parallelism of the profiles of all the gases, i.e. H20, CO, COa, NO and N, is worth noting, as it is implied that they all originate from the same groups of reactions. The presence of N2 and NO among the gases evolved indicates that the nitro group of PNP was reduced at the interface of the system, which in turn would give additional amounts of CO, CO, and H,O (Table 2). These redox processes are exothermic, and heat evolution from the system was studied by differential scanning calorimetry (DSC) up to 1100 K in the same experimental conditions as the TPD-MS experiments. The equipment used was a Perkin-Elmer, Model 3600. The DSC curve obtained is depicted in Fig. 10. At the temperatures corresponding to the above peaks (550 and 700 K) two exothermic peaks are observed whose values are -59 and - 63 kJ/mol PNP chemisorbed, respectively, which corroborate the occurrence of the above reactions. From the amounts of NO and Nz given in Table 2 and the amount of PNP chemisorbed (the difference between X and the PNP physisorbed that evolved up to 450 K), all the nitro groups present in the PNP chemisorbed participate in the redox reactions that take place at 550 and 700 K. (iii) Above 750 K, the DTG profile shows a continuous increase while the MS profile remains almost parallel to the abscissa, indicating that a large amount of heavy compounds are released. This can be explained by increased volatility of the heavy compounds formed on the surface of the activated carbon compared to other systems, resulting in the evolution of greater amounts in this temperature range, or it could be a consequence of the above redox reactions causing some degree of depolymerization of the carbon surface. With respect to the light gases (Fig. 5)

2000

SW

W
-lOOO-

The weight loss of this system determined by TG up to 1100 K was 285 mg g- C, comparing this value with the weight of adsorbed p-nitrophenol (180 mg/g C) it is clear that beside p-nitrophenol, part of the carbonous matrix is eliminated. These results also confirm that the activated carbon is attacked by the nitro groups during its thermal regeneration. The results obtained in this work, together with those previously published[2,5-71 on the thermal desorption of different phenolic compounds from activated carbons enable us to draw the following conclusions. During the adsorption process of the phenolic compound on activated carbons from aqueous solutions this is physisorbed and chemisorbed. When this activated carbon-phenolic compound system is heat-treated up to 1100 K in an inert gas flow, the physisorbed phenol evolves at a low temperature from the surface of the carbon and is deposited at the outlet of the reactor either as itself or as a heavy compound. At the same time some of the physisorbed phenol can be transformed to chemisorbed phenol. This transformation is favoured by: the experimental conditions (amount of sample, gas flow, heating rate), readsorption of the phenol compound and the formation of radical species. The fraction of phenolic compound chemisorbed is converted to: light gases and heavy products (in some cases) that evolve from the surface of the activated carbon, and also to a carbonaceous residue or polymer that remains on the surface of the carbon. In the production of light gases, the oxygen surface complexes of the activated carbon play an important role acting as cracking centers for the phenolic compound molecules. In all cases, except in that of PNP, the total amount of light gases evolved is quite similar, with a higher oxygen content in these gases than in the chemisorbed phenolic compound. The behaviour of PNP is different due to the attack of the nitro group on the surface of the carbon. Pyrolysis of chlorophenols in an inert atmosphere has been shown to give a high yield of graphite Aake[ 141, the formation of a carbonaceous residue or polymer on the activated carbon surface in all cases, except in the PNP thermal desorption, could therefore be related with the condensation of large aromatic radicals into an extended sp structure. If this is so, the formation of this residue would be related to the H, evolution. Thus, in the case of the activated carbon-PC system the amount of H, evolved is the greatest (see Table 2), which also corresponds to the highest amount of residue left. 4.5 Adsorption-regeneration cycles The adsorption capacity of the activated carbon APlO for each phenolic compound after its regeneration has also been studied. For this purpose, the spent activated carbon was heat-treated in dry N, flow

-2500. ;.:a

-40001 273

473

6'3 T W)

873

1073

Fig. 10. DSC of the APlO-p-nitrophenol

system.

Thermal regeneration of an activated carbon APlO-p-cresol system, was reduced to 50%, further cycles in spite on the surface in this the reduction of the after seven cycles for is around 80%.

1423 since after the fourth cycle this remaining almost constant for of the fact that the residue left system was the highest. Finally, adsorption capacity of APlO both phenol and p-nitrophenol

Acknowledgements-Financial (Project No. AMB92-1032) Joint Research Programme acknowledged.


0 I 2 3 4 5 6 7

support from CICYT and the Spanish-French (No. 223B) is gratefully

Number of cycles

REFERENCES
1. M. Suzuki, D. M. Lusic, 0. Koyama and K. Kawazoe,

Fig. 11. Variation of the adsorption capacity of the activated carbon APlO as a function of the adsorption-regeneration cycle. Phenol, A; m-aminophenol, 0; p-cresol, 0; p-nitrophenol, 0. (100cm3 min-) up to 973 K (heating rate 20 k min-) and this temperature was maintained for 1 hour. The regenerated samples were again saturated with the corresponding phenolic compound, determining their new adsorption capacity. These adsorption-regeneration cycles were determined up to 7 times. The results obtained as a function of the number of cycles are depicted in Fig. 11. The value of cycle 0 corresponds to the adsorption capacity of the original activated carbon APlO. The capacity of APlO to adsorb phenolic compounds decreases as the number of adsorption-regeneration cycle increases. The extent of this decrease depends on the phenol type. Thus, the most pronounced decrease occurs with the PNP system whose adsorption capacity after the three first cycles undergoes a marked decrease from 196 to 39 mg g- C, showing a negligible value after the sixth cycle. The lowest decrease in adsorption capacity with the adsorption-regeneration cycles is detected for the

Gem. Eng. Sci. 33, 271 (1978). 2. P. Magne and P. L. Walker, Jr, Carbon 24, 101 (1986). 3. M. V. L6pez-Ram&, C. Moreno-Castilla, J. RiveraUtrilla, and R. Hidalgo-Alvarez, Carbon 31, 815 (1993). %. Carrasco-Marin, M. V. L6pei4. C. Moreno-Castilla, 5. M. A. Ferro-Garcia, 6. 7. 8. 9. 10. 11. 12. 13. 14. 15.
and J. Rivera-Utrilla. Carbon 33. 845 (1995). E. &era-Hidalgo, J. RiveraUtrilla, C. Moreno-Castilla and J. P. Joly, Carbon 31, 857 (1993). J. Rivera-Utrilla, M. A. Ferro-Garcia, C. MorenoCastilla and J. P. Joly, Carbon 32, 743 (1994). M. A. Ferro-Garcia, J. P. Joly, J. Rivera-Utrilla and C. Moreno-Castilla, Langmuir, submitted for publication. F. Carrasco-Marin, M. V. L6pez-Ram6n and C. Moreno-Castilla, Langmuir 9, 2758 (1993). C. Moreno-Castilla, F. Carrasco-Marin and M. V. L6pez-Ram6n, Langmuir 11, 247 (1995). D. Bianchi and J. P. Joly, Bull. Sot. Chim. Fr. 4, 664 (1985). D. Bianchi and J. P. Joly, Bull. Sot. Chim. Fr. 4, 668 (1985). D. Bianchi and J. P. Joly, Spectra 2000 13, 101 (1985). C. A. Lebn y Le6n, J. hi. Solar, V. Calemma anh L. &. Radovic. Carbon 30. 797 (1992). S. Cookk and M. G. Labks, Carbon 32, 1055 (1994). J. S. Mattson, H. B. Mark, Jr, M. D. Malbin, W. J. Weber, Jr and J. C. Critenden, J. Col. Interface Sci. 31, 116 (1969). Rambn

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