Bioresource Technology 98 (2007) 30173025

Bench-scale and packed bed sorption of methylene blue using treated olive pomace and charcoal
F. Banat a, S. Al-Asheh
a

b,*,1 ,

R. Al-Ahmad a, F. Bni-Khalid

Department of Chemical Engineering, Jordan University of Science and Technology, Irbid-22110, Jordan b Department of Chemical Engineering, University of Qatar, Doha, Qatar Received 19 June 2006; received in revised form 14 October 2006; accepted 14 October 2006 Available online 8 December 2006

Abstract A combination of olive pomace after solvent extraction and charcoal produced from the solid waste of olive oil press industry was used as an adsorbent for the removal of methylene blue (MB) dye from aqueous solutions. Batch tests showed that up to 80% of dye was removed when the dye concentration was 10 mg/ml and the sorbent concentration was 45 mg/ml. An increase in the olive pomace concentration resulted in greater dye removal from aqueous solution, and an increase in MB dye concentration at constant adsorbent concentration increased the dye loading per unit weigh of adsorbent. In the kinetic of the adsorbent process, the adsorption data followed the second-order kinetic model better than rst order kinetic model. Charcoal showed higher sorption capacity (uptake) than that of olive pomace. In the xed bed adsorption experiment, the breakthrough curves showed constant pattern behavior, typical of favorable isotherms. The breakthrough time increased with increasing bed height, decreasing ow rate and decreasing inuent concentration and methylene blue dye uptake. The uptake of MB dye was signicantly increased when a mixture of olive pomace and charcoal was packed in the column in a multi-layer fashion. Dierent models were used to describe the behavior of this packed-sorption process. 2006 Elsevier Ltd. All rights reserved.
Keywords: Bentonite; Adsorption; MBD; Microwave; Natural; Kinetics; Isotherm

1. Introduction The disposal of liquid euent from various industries, such as textile, paper, plastics, leather, food, and cosmetics, receives special attention by environmentalists. These euents contain number of contaminants; among these are the colored dye materials. Besides having possible harmful eects, dying materials in water are aesthetically unpleasant. Although not strongly hazardous, methylene blue (MB), one of the well-known dye materials, can have various harmful eects. For example, during inhalation, it can give rise to short periods of rapid or dicult breathing,
*

Corresponding author. E-mail address: alasheh@qu.edu.qa (S. Al-Asheh). On leave from Jordan University of Science and Technology.

while ingestion through the mouth produces a burning sensation and may cause nausea, vomiting, diarrhea and gastritis (Albanis et al., 1988). The possible methods of dye removal from industrial euents include adsorption, chemical occulation, chemical oxidation, froth oatation, ozonation, reverse osmosis and biological techniques (Robinson et al., 2001). The most widely used method for removing methylene blue dye from aqueous solutions is adsorption, where activated carbon being the most eective material used for this purpose. However, the expensiveness and regeneration problem of activated carbon have motivated many workers to search for low-cost potential adsorbents. Numerous investigations have been carried out to develop the potential application of readily available and inexpensive materials. Examples of these materials include fertilizer waste (Srivastava

0960-8524/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2006.10.023

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et al., 1997), bentonite clay (Banat et al., 2000), spent bleaching earths (Pollard et al., 1992), agricultural byproducts (Johns et al., 1998), olive stones (Alaya et al., 2000), and date pits (Banat et al., 2003). Commercially available activated carbons are usually derived from natural materials such as wood or coal. One of the candidate sources of activated carbon is the solid waste of the olive oil processing. This would also result in waste minimization of the solid waste resulted from the olive oil industry. Jordan is one of the olive oil producing countries in the world. The olive tree has nutritional, social and economic importance in the life of Jordanian people. According to a report published by the Ministry of Agriculture in Jordan, olive trees are planted on more than 6.16 104 ha of land, with an estimated number of more than 8.12 106 trees (Ministry of Agriculture, 1997). The manufacturing of olive oil produces two kinds of euents, a solid waste (pomace) and a liquid. Pomace is the ground esh and pits after pressing. Any oil that has not been removed by pressure can be extracted using steam and solvents. The pomace is generally swallowed by means of controlled spreading on agricultural soil. Only small quantity of the olive mill solid residue that is used as natural fertilizer, combustible and additive in animal food, thus, it is of advantageous to nd other applications for such a solid waste. In this work, olive pomace that remains after pressing is rst treated with chemical solvents to extract the residual oil, washed, dried and then used for dye adsorption either alone or mixed with commercial charcoal produced from the solid waste of olive mills. MB dye experiments were carried out on bench-scale batch and packed-column operations. Packed column operation is preferred over the bench-scale batch operation for the removal of micro-pollutants when dealing with large volumes of wastewater. The equilibrium isotherms and kinetic characteristics of methylene blue dye adsorption using the above-mentioned were investigated using bench-scale batch tests. In packed bed tests, the eects of the typical column parameter, such as column height, inuent ow rate, packing materials and inuent concentration, on the performance of the column were determined.

supplied by BDH was used as adsorbate and was not puried prior to use. 2.2. Batch sorption tests The batch sorption tests were performed as follows. Known weights of olive pomace were transferred into dark glass bottles containing 30 ml of aqueous solutions of methylene blue dye at specied concentration, such that the adsorbent concentration was made in the range 0.3 0.45 mg/ml. The mixtures were agitated in a shaker and samples were taken at xed time period, namely, 0.5, 1, 2, 3, 4, 10 h, in order to study the kinetics of the adsorption process on the olive pomace and the charcoal. In other studies, equilibrium was allowed to attain and the bottles were removed from the shaker at the end of the experiments. The solution was separated from the samples via centrifugation. The concentration of MB was determined using Spectronic spectrophotometer. All measurements were done at the wavelength corresponding to the maximum absorbance at 612 nm using distilled water as a blank. After determination of dye concentration in the batch sorption tests, which is designated as Cf (mg/l), the extent of dye removal was calculated as: Q Ci Cf V M 1

where Q is dye uptake (mg dye/g adsorbent), Ci is the initial dye concentration (mg/l), M is the quantity of adsorbent employed (mg) and V is the volume of the suspension (ml). 2.3. Packed-bed sorption tests Packed-bed operation was conducted in this work using column packed with olive pomace and charcoal produced from the solid waste of olive oil industry. The column, of dimension 20 cm height 1.5 cm ID and made of plexy glass, was designed with four ports along the height of the column (each 4 cm a part). These ports, as well as the two ends of the column, were connected to lter discs, and being tted with 0.45 lm cellulose lter paper; an O-ring and plug stoppers were also used as tting items. The column was packed with about 11.96 g of adsorbent and methylene blue dye solution, at concentrations ranging from 10 to 40 mg/l, was pumped upwards through the column at set ow rates. Samples were collected periodically from the top of the column as well as form the ports and analyzed for residual concentration of methylene blue dye. The state at which the euent and the inuent concentrations were equal is designated as the steady state, were the experiment is terminated. 3. Models used A number of models are available for the kinetics of adsorption process. These models describe the sorption

2. Methods 2.1. Materials The olive pomace is supplied by one of the olive oil production plants in Jordan. Solvent extraction of residual oil in olive pomace was performed using a Soxhlet extractor with n-hexane. Thereafter, the solid material was washed and dried in an oven to be used in adsorption tests. Commercial charcoal produced from the solid waste of olive pomace was bought from the market and integrated into particles size in the range 24 mm to be used in the adsorption tests. Methylene blue (MB) dye, of analytical grade,

F. Banat et al. / Bioresource Technology 98 (2007) 30173025

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rate equation as the rate of solutes transfer from liquid suspension to the surface of the sorbent. These models are normally used in order to determine the existence of particular mechanism for the sorption process, i.e. chemisorption or physical adsorption. The simplest one is the rst order rate equation can be written as (Ho and Chiang, 2001): dq k 1 qe q dt Upon integration, this equation yield:   q qt ln e k 1 t qe 2

through, u is the supercial liquid velocity (cm/min), and k is the adsorption rate constant [(mg min)/cm3]1. Application of the BDST model requires specication of the breakthrough time, which was selected arbitrarily in this work as the time corresponding to C/C0 = 0.1. Thomas model is another kinetic model which has been originally derived the from Bohart and Adams analysis. The linearized form of this model (Reynolds and Richards, 1996) can be written as:   C0 kq M ln 1 0 kC 0 t 8 Q C where k here has the same meaning as that in Eq. (7), q0 is the maximum adsorption capacity of the adsorbent (mg/g), M is the mass of adsorbent (g), Q is the volumetric ow rate (ml/min) of the solution, and t (min) is service time of the column under given conditions. The parameters N0, k, and q0 in both of the above mentioned models are normally obtained from the experimental data of the breakthrough curves and can be used in the design of a full-scale adsorption bed. Another model used in this work is the one which was recently proposed (Yan et al., 2001) and can be written in its a linearized form as     C0 kQ kQ kq0 Q ln 1 ln V ln 9 C0 C0 M C where V is the throughput volume (ml) and other parameters are the same as previously mentioned. 4. Result and discussion 4.1. Kinetics of batch the sorption process The objective of adsorption kinetic study is to investigate the possible mechanisms for the sorption process and to determine the time required to attain equilibrium. This was examined for the sorption of MB on each of the sorbents olive pomace and charcoal using series of measurements extending from 2 to 10 h at 25 C. The results are shown in Fig. 1; it seen that the rate of adsorption is relatively fast for both adsorbents. However, the time needed to attain equilibrium is longer when using charcoal ($6 h) than that of olive pomace ($4 h). However, at equilibrium, the amount of MB uptake is higher for charcoal than that of olive pomace at the same conditions. The kinetics data of Fig. 1 were analyzed using the linearized models presented in Eqs. (3) and (6). Representations of the experimental data by these models are shown in Figs. 2A and 2B, respectively. The parameters of the models are listed in Table 1. Obviously, the kinetics data for both models poorly represented by the rst order model; but, they are highly matched by the pseudo-second order kinetics model. Kinetics data which follows pseudosecond order models gives an indication of the chemisorptions nature of the adsorption process.

where q(t) and qe, in mg/g adsorbent, are the MB uptakes at time t (h) and at equilibrium, respectively; k1 is the rst order sorption rate constant. The later can be obtained from the experimental data by plotting ln[(qe q(t))/qe] versus t, which should results in a straight line the slope of which is k1. The other sorption kinetics model is pseudo-second order, which can be expressed in dierential form as: dq k 2 qe q2 dt this upon integrating gives: 1 1 k2t qe qt qe 5 4

where k2 is the pseudo-second-order rate constant of sorption. Eq. (5) is often written as: t 1 1 t qt k 2 q2 qe e 6

In this case, the rate constant k2 can be obtained experimentally by plotting t/q(t) versus t gives, which gives a straight line with intercept of 1=k 2 q2 and slope 1/qe. e In conducting packed-bed sorption experiments, normally the results are presented in terms of concentration time prole or breakthrough curve. From such curve, the maximum sorption column capacity can be determined. Such parameter is important for the characteristic of any sorption process. This can be done by applying certain mathematical models. The simplest model, known as the bed depth-service-time model (BDST), is based on Bohart and Adams theory. This model assumes that the rate of adsorption is controlled by the surface reaction between the adsorbate and the unused capacity of the solid. The BDST model gives a linear relationship between the time required to reach the desired breakthrough concentration (tB) and the bed depth (Z) (Reynolds and Richards, 1996), that is:   N0 1 C0 tB Z ln 1 7 kC 0 C0u CB where N0 is the initial adsorptive capacity per unit volume of bed (mg/cm3), C0 is the bed inuent concentration (mg/ l), CB is the desired concentration of solute at break-

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2.0 1.8 1.6

F. Banat et al. / Bioresource Technology 98 (2007) 30173025

600

500

Olive pomace Charcoal

MB uptake (mg/g)

1.4 1.2

400

t/q(t)
Olive pomace Charcoal

1.0 0.8 0.6 0.4 0.2 0.0 0 100 200 300 400 500 600

300

200

100

100

200

300

400

500

Time (min)
Fig. 1. Kinetics of MB uptake by olive pomace and charcoal. Sorbent concentration: 2 mg/ml; MB concentration: 10 mg/l.

t (min)
Fig. 2B. Representation of the kinetics data by the pseudo second-order model (Eq. (6)).

Table 1 Rate constants and R2 values for the rst and second order kinetic models Adsorbent First order model k1 R2 0.888 0.964 Pseudo-second order model k2 0.1220 0.0906 R2 0.999 0.999

-1

Olive pomace Charcoal

Charcoal Olive pomace

0.000805 0.01611

ln(q -q)

-2

12

Final MB concentration in solution (mg/l)

10

-3

-4

100

200

300

400

500

t (min)
Fig. 2A. Representation of the kinetics data by the rst-order model (Eq. (3)).

4.2. Eect of sorbent concentration Examination of the eect of olive pomace concentration on the removal of MB dye from aqueous solution showed that the concentration of MB dye were further decreased with the additional amounts of olive pomace in the suspension from 0.3 to 45 mg/ml (Fig. 3). The reason for such behavior is attributed to the larger number of binding sites on the adsorbent available to the dye. However, it can be shown that the uptake per unit amount of adsorbent decreases with the increase in adsorbent concentration, at a given initial MB dye concentration (10 ppm). These results are in agreement with the data published for other plant waste adsorbents (Al-Asheh and Duvnjak, 1998). According to the data of this work,

10

20

30

40

50

Time (min)
Fig. 3. Eect of sorbent (olive pomace) concentration on the equilibrium (nal) concentration of MB. Initial MB concentration: 10 mg/l.

at initial MB concentration of 10 mg/l, the maximum amount of MB removal is 80% is achieved when using 45 mg/ml of olive pomace. 4.3. Eect of MB concentration The eect of MB concentration on its uptake by olive pomace and charcoal was studied at constant temperature

F. Banat et al. / Bioresource Technology 98 (2007) 30173025

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4.4. Packed bed sorption of MB As the capacity of olive pomace and charcoal towards methylene blue dye sorption were found to be comparable to other sorbents, it is of interest to examine the performance of these sorbents in a ow-through sorption column system. The eects of such parameters, column height, inuent ow rate, packing materials, inuent concentration of MB, on the performance of the column were considered.
Olive pomace Charcoal

60

50

MB uptake (mg/g)

40

30

20

4.5. Eect of bed height The concentration variation along the column height was studied by introducing 40 mg/l MB solution at a rate of 60 ml/min. Samples were collected from ports located in the column at distances of 4, 8, 12, 16, 20 cm (top of the column) from its bottom. The results (Fig. 5) presented as the ratio of the euent to the inuent concentration (C/C0) versus bed depth at dierent time intervals; i.e. breakthrough curves. Initially, the feed solution was contact with the fresh adsorbent at the bottom of the column. Methylene blue dye was adsorbed progressively on the sorbent as it owed upward. As more uid fed to the column, the bottom portion of the adsorbent becomes saturated with methylene blue dye; thus, the adsorption zone moves upwards. Therefore, the concentration of solute in the lower portions of the packed bed is usually higher than that in the top portions. The results presented in Figs. 5A and 5B show the breakthrough curves at dierent bed heights using charcoal and olive pomace as packing materials, respectively. Obviously, the breakthrough time varies with the bed height; where the breakthrough concentration being reached sooner at the lower ports of the column than at the higher

10

50

100

150

200

Final MB concentration in solution (mg/l)

Fig. 4. Eect of nal dye concentration on its uptake by olive pomace and charcoal. Sorbent concentration: 5 mg/ml.

25 C using 5 mg/ml of each of the sorbents. The results obtained showed that the increase in MB dye concentration resulted in an increase in the MB dye uptake (Fig. 4). This is true for both of the sorbents. The increase in the MB uptake is linear at low concentrations, but becomes immeasurable slow when the state platitude is attained at high concentrations; this characterizes the monolayer coverage nature of solute by the sorbent. Comparison of the adsorption capacity of methylene blue by the sorbents used in this work and those reported elsewhere is shown in Table 2. It is seen that the sorption capacity of the sorbent used in this work is still higher than some of the available ones in the literature.

Table 2 Materials used as adsorbents for methylene blue Adsorbent Wood Cotton waste Bentonite Chrome sludge Activated olive stones Activated furniture (800 C) Activated sewage char (800 C) Activated tyres (850 C) Fly ash Zeolite Amorphous silica Banana peel Orange peel Pure kaolin Activated tire char Raw date pits Activated date pits Olive pomace Charcoal Capacity (mg/g) 84 24 150 0.51 22.1 200 120 130 1.3 12.7 26.5 20.8 18.6 15.6 227 80.3 17.3 42.3 62.7 Reference McKay and Poots (1986) McKay and Poots (1986) McKay and Poots (1986) Lee et al. (1996) Alaya et al. (1999) Saniz-Diaz and Griths (2000) Saniz-Diaz and Griths (2000) Saniz-Diaz and Griths (2000) Woolard et al. (2002) Woolard et al. (2002) Woolard et al. (2002) Annadurai et al. (2002) Annadurai et al. (2002) Gosh and Bhattacharyya (2002) Lin and Teng (2002) Banat et al. (2003) Banat et al. (2003) This work This work

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1.2 4 cm 8 cm 12 cm 16 cm 20 cm

F. Banat et al. / Bioresource Technology 98 (2007) 30173025

1.2

1.0

1.0

0.8

0.8

C /C0

C /C0

0.6

0.6
20 ml/min 45 ml/min 60 ml/min

0.4

0.4

0.2

0.2

0.0 0 100 200 300 400 500 600 700

Time (min)

0.0

20

40

60

80

100

120

140

160

180

200

Time (min)
Fig. 6A. Eect of inuent ow rate on the breakthrough curves for MB dye sorption by olive pomace. Bed depth: 8 cm; inuent MB concentration: 40 mg/l.

Fig. 5A. Eect of bed height on beak-through curves for sorption of MB by charcoal. Inuent ow rate: 60 ml/min; inuent MB concentration: 40 mg/l.

1.2

1.2

1.0

1.0

0.8

0.8

C /C0

0.6 4 cm 8 cm 12 cm 16 cm 20 cm

C /C0

0.6 20 ml/min 45 ml/min 60 ml/min

0.4

0.4

0.2

0.2

0.0 0

20

40

60

80

100

120

140

160

0.0

Time (min)
Fig. 5B. Eect of bed height on beak-through curves for sorption of MB by olive pomace. Inuent ow rate: 60 ml/min; inuent MB concentration: 40 mg/l.

50

100

150

200

250

300

Time (min)
Fig. 6B. Eect of inuent ow rate on the breakthrough curves for MB dye sorption by olive pomace. Bed depth: 20 cm (top of the column); inuent MB concentration: 40 mg/l.

ports. This is a typical trend for the eect of bed height on the breakthrough concentration (or time). 5. Eect of inuent ow rate To study the eect of ow rate on the breakthrough curves, methylene blue dye solution of 40 mg/l concentration were pumped at dierent ow rates, viz. 20, 45, and 60 ml/min, through the olive pomace packing column. Breakthrough curves at two port locations along the column (8 cm and 20 cm) were obtained for each of these ow rates. As expected, the breakthrough time (the position at C/C0 = 0.1) increased with decreasing ow rate (Fig. 6). The MB dye uptake of the olive pomace column at each ow rate, as estimated from the material balance at steady state, is shown in Table 3. Larger volumes of methylene blue dye solution were required to attain a steady state when using larger ow rates. The MB dye uptake by the

column is higher at high ow rates than that at low ow rates; however, this is opposite for the percentage of methylene blue dye removal. The representations of the breakthrough data, i.e. breakthrough time (also called service time) versus bed depth, were represented by the three previously mentioned models, Eqs. (7)(9), at dierent ow rates. The linear plots resulted from these three models are shown in Figs. 7A, 7B and 7C, respectively. These plots, with the R2 values displayed in Table 4, indicate the validity of the previously mentioned model for the experimental data presented in this work. The model parameters were determined from the intercept and the slope of these plots. The variations of these parameters, which can be used for the evaluation of the sorbent performance, are displayed in Table 4 for the three models. The increase in N0 can be attributed to the larger mass transfer driving force at high ow rates.

F. Banat et al. / Bioresource Technology 98 (2007) 30173025 Table 3 Eect of inuent ow rate on MB dye uptakea Flow rate (ml/min) 20 45 60
a

3023

Total volume pumped (l) 4.0 8.1 9.0

MB dye uptake (mg/g) 8.55 15.24 16.17

Removal (%) 62.25 55.00 52.25

Q= 20 ml/min Q= 45 ml/min Q= 60 ml/min

ln(C/(C0-C))

Inuent MB concentration: 40 mg/l.

180 160 140 120 100 80 Q=20 m/min Q=45 ml/min Q=60 ml/min

-1

-2

Service time (min)

-3 7.8

8.2

8.4

8.6

8.8

9.2

ln V
Fig. 7C. Yan et al. (Eq. (9)) representation.
60 40 20 0 0 2 4 6 8 10 12 14 16 18 20 22

in Table 2. The value of the kinetic constant, k, obtained by the three models increased with increasing the ow rate. This demonstrates that the mass transfer resistance of diffusivity in liquid layer can not be neglected under the conditions studied.
Bed depth (cm)
Fig. 7A. BDST model representation.

5.1. Eect of initial concentration The eect of the initial concentration of MB dye on the breakthrough curves was studies using olive pomace as packing material at a xed feed ow rate of 60 ml/min. The concentrations studies were 10, 20 and 40 mg/l. Breakthrough curves at the top of the column were obtained for each of these concentration (Fig. 8). Similarly, the breakthrough point decreased with increasing the feed solute concentration. Increasing the feed concentration by a factor of two, i.e. from 10 to 20 mg/l, only slightly decreased the breakthrough time while increasing the feed concentration from 20 to 40 mg/l caused signication decrease in the value of the breakthrough time. Hence, in order to achieve the same operating capacity, it is either necessary to lower the feed ow rate when using concentrated solutions or to use columns in a series arrangement. The uptake of methylene blue dye as a function of feed concentration was calculated by performing a simple mass balance. The results are presented in Table 5. It is seen that the amount of MB dye removal (%) increases with decreasing the inuent concentration. A higher uptake of MB dye in columns packed with olive pomace was observed at higher inuent MB dye concentrations. The fact that the mass transfer driving force increases with increasing the feed concentration is the reason beyond such results. A comparison between column capacity and that of batch bench scale one is shown in Table 6. It is observed that packed-bed capacity is more than the batch bench-scale

Q= 60 ml/min Q=45 ml/min Q=20 ml/min

ln((C0/C)-1)

-1

-2

-3

-4

-5 0 50 100 150 200 250

t (min)
Fig. 7B. Thomas model representation.

The maximum adsorption capacities at dierent feed ow rates, as obtained from Thomas model, N0 (Table 4) as we well as from Eq. (9), q0, are comparable values present

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F. Banat et al. / Bioresource Technology 98 (2007) 30173025

Table 4 Model parameters and R2 values (Eqs. (7)(9)) for sorption of MB by olive pomace at dierent ow ratesa Flow rate (ml/min) BDST mode N0 (mg/ml) 20 45 60
a

Thomas model k (ml/mg min) 0.0366 0.0459 0.0785 R

2

Eq. (9) q0 (mg/g) 8.542 17.557 18.218 R

2

k (ml/mg min) 1.900 2.163 2.248

k (l/mg min) 0.6013 1.079 1.334

q0 (mg/g) 9.00 17.9 20.18

R2 0.996 0.9947 0.9926

6.071 8.358 8.496 Inuent MB concentration: 40 mg/l.

0.974 0.984 0.997

0.9954 0.984 0.9666

1.2

1.2 Packing A Packing B Packing C Packing D

1.0

1.0

0.8

0.8

C/C0

0.6 10 mg/l 20 mg/l 40 mg/l

C /C0
0 50 100 150 200 250

0.6

0.4

0.4

0.2

0.2

0.0

0.0

100

200

300

400

500

600

700

Time (min)
Fig. 8. Eect of inuent MB concentration on the breakthrough curve at the top of the column. Inuent ow rate: 60 ml/min.

Time (min)
Fig. 9. Eect of packing material on the breakthrough curve of MB sorption in xed bed. A: half pomace + half charcoal; B: multilayer of pomace and charcoal arrange in the order: 1/4 pomace, 1/4 charcoal, 1/4 pomace, 1/4 charcoal; C: mixture of charcoal and pomace; D: charcoal.

Table 5 Eect of inuent concentration of MB dye on its uptake by the olive pomace packed-beda Inuent concentration (mg/l) 10 20 40
a

Total volume pumped (l) 11.88 10.80 9.00

MB dye uptake (mg/g) 7.12 10.16 16.17

Removal (%) 70.1 55.0 52.3

Flow rate, Q = 60 ml/min.

Table 6 Comparison between batch bench scale sorption packed-bed and capacitiesa Initial concentration (mg/l) 10 20 40 40
a

Batch bench-scale capacity (mg/g) 1.02 3.27 7.54 38.34

Packed-bed capacity (mg/g) 6.02 8.78 13.85 74.00

centration gradient at the interface of the adsorption zone as it passes through the column, while the concentration gradient decreases with time in the batch bench scale operation. These results are in agreement with the ndings of Al-Asheh and Duvnjak (1998). Although regeneration process is not conducted in this work, however, low uptake of methylene blue is expected at low pH values due to the presence excess H+ ions competing with the dye cation MB+ for the adsorption site. Thus desorption of methylene blue dye can be performed by passing acidic solution through the column. Since adsorption of dye is very low at low pH, so desorption occurred at low pH values. 5.2. Eect of multi-layer packing material To study the eect of packing material on the performance of packed-bed sorption operation, dierent MB solutions of 40 mg/l concentration, at 60 ml/min ow rate, were introduced into dierent columns each with dierent packing materials (Fig. 9). The breakthrough curves presented in Fig. 9 correspond to: A: half pomace and half charcoal; B: multilayers of pomace and charcoal arrange in the order: 1/4 pomace, 1/4 charcoals, 1/4 pomace, 1/4 charcoals; C: a mixture of pomace with charcoal; D: charcoal only. It can be noticed that bed packed with material

(olive pomace) (olive pomace) (olive pomace) (charcoal) Flow rate: 60 ml/min.

capacity. A more plausible explanation is the inherent dierence in the nature of continuous feed to the packed column compared to the xed amount of solution in the bench scale batch operation. A higher capacity of packed operation is established by a continuously increasing con-

F. Banat et al. / Bioresource Technology 98 (2007) 30173025 Table 7 Eect of packing material and method of packing on the removal of MBa Packing material Material Material Material Material
a

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References
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Total volume used (l) A B C D 18.6 20.4 21.6 36.0

MB dye uptake (mg/g) 46.12 47.21 48.02 74.00

Removal (%) 75.0 70.0 67.5 62.2

Inuent concentration: 40 mg/l; inuent ow rate: 60 ml/min.

D has the highest breakthrough point, i.e. 480 min, while bed packed with material A has the lowest breakthrough point, i.e. 210 min, and there is no big dierence between beds packed with material B or material A. However, different arrangements and percentage of same packing materials caused dierent breakthrough point. Table 7 shows that material D has the highest MB dye uptake, while no big dierence in the values of the uptakes for columns packed with materials A, B and C. This could be due to the constituents of charcoal, which contains a high percentage of carbon. In general, each of the adsorbents used has certain contribution to the amount of dyes being adsorbed. According to the results of this work, charcoal has more anity to adsorb dyes. The idea of using mixture of two adsorbents, e.g. charcoal and olive pomace, or more is to minimize the amount of charcoal used. 6. Conclusions The removal of methylene blue dye from its aqueous solutions by olive pomace and charcoal was studied in batch-suspension and packed bed experiments. The batch-suspension tests showed that the MB uptake increases with increasing olive pomace concentration and that equilibrium was attained within 7 h. The kinetics data followed the second order kinetics model indicating the chemisorptions nature of the process. A column packed with olive pomace can reasonably be used for the removal of MB dye from aqueous solution. Increasing column height, decreasing inuent ow rate and decreasing MB inuent MB concentration, all resulted in an increase in the breakthrough time. The characteristics of the breakthrough curve can be improved by packing the column with multilayers of olive pomace and charcoal. The three models used in this work for the packed bed operation work t the experimental reasonably well. The sorption process implemented in this works is industrially feasible. Since materials used as adsorbents are widely available in the country and can be packed in an industrial column used for treatment of an euent containing methylene blue treatment in a wastewater treatment process; of course, this requires scale-up of the column used in this work.