Environmental Engineering and Management Journal

January/February 2009, Vol.8, No.1, 173-181

http://omicron.ch.tuiasi.ro/EEMJ/

Gheorghe Asachi Technical University of Iasi, Romania

______________________________________________________________________________________________

ADSORPTION OF N-HEXANE VAPORS ONTO NON-FUNCTIONALIZED HYPERCROSSLINKED POLYMERS (HYPERSOL-MACRONETTM) AND ACTIVATED CARBON: EQUILIBRIUM STUDIES
Adela Marilena Buburuzan Halea, Cezar Catrinescu, Matei Macoveanu
Gheorghe Asachi Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection, Department of Environmental Engineering and Management, 71 Mangeron Blvd., 700050 Iai, Romania

Abstract
Two non-functionalized hypercrosslinked polymeric resins type Macronet (MN 202 and MN 250) were employed to remove nhexane vapors from gas phase. A comparison of the equilibrium behavior of these hypercrosslinked resins and a bituminous granular activated carbon was made. The initial n-hexane concentration in the air stream ranged from 2100 to 4500 ppm and the adsorption temperatures were 30C, 40C and 50C. The results showed that the MN 250 presents the higher adsorption capacities of n-hexane, in all studied conditions. The experimental results were fitted to the Freundlich, Langmuir and DubininRaduchkevich equation isotherms, to obtain the characteristic constants of each model. The maximum adsorption capacity for nhexane, determined by using these model isotherms, decreased in the following order: MN 250 > MN 202 AC 20.

Key words: VOCs, hexane, adsorption, activated carbon, hypercrosslinked polymeric resins, isotherm 1. Introduction Denomination of volatile organic compounds (VOCs) refers to organic compounds which vapor pressure is at least 0.01 kPa at 20C. VOCs are also characterized by their low water solubility. Volatile organic compounds (VOCs) in ambient air are associated with emissions from a range of sources as motor vehicle exhaust, motor vehicle fuel evaporative losses, industrial activities, petroleum refining, petroleum storage and dispensing facilities, leakage of petrol and diesel fuel from underground storage tanks, surface coating and solvent use such as thinner, degreasers, cleaners, lubricants, domestic wood heaters, biomass burning, environmental tobacco smoke, use of solvents and glues and cleaners in arts and crafts (Hinwood et al., 2006; Kawashima et al., 2006; Serrano and Gallego, 2006). Volatile organic compounds may cause health problems for humans or damages to environment. It is well established that the degradation of volatile

organic compound in the troposphere leads to the production of a range of secondary pollutants which may have a harmful impact on human health and on the environment. They almost always contribute to ground level ozone formation and ozone depletion in the stratosphere, and in addition are odorous and sometimes toxic. In other words, they react in sunlight with other pollutants such as nitrogen oxides to form ozone and the other compounds (known as photochemical oxidants), which make up photochemical smog (Guillemot et al.; 2008, Jenkin et al., 1997). For this reason VOCs are being subject to increasingly severe constrains; in Europe, VOCs are controlled through the EU Directive 1999/13/EC on the limitation of emissions of volatile organic compounds. Therefore, industries either reconsider the production process to reduce their emissions or more frequently, set up an end-of-pipe treatment unit. There are a number of existing and emerging technologies for end-of-pipe VOC control: thermal or catalytic oxidation, biological treatments (which is

Author to whom all correspondence should be addressed: e-mail: adelahaleta@ch.tuiasi.ro; haletaadela@yahoo.co.uk

Buburuzan Halea et al./Environmental Engineering and Management Journal 8 (2009), 1, 173-181

classified in destruction technique) and condensation, adsorption, membrane separation, or absorption (which is classified in recovery technique) (Heymes et al., 2006; Liu et al., 2008; Pagans et al., 2006). Hexane is one of the volatile organic compounds that represent the compounds from nalkanes class, and its widely used in various domains and activities: as a solvent for inks or paints and protective coatings systems, the cleaning agent for the metals and plastics components, extraction agent for vegetable oils from oil seeds, solutions and intermediate in the synthesis of other chemical products, reagent in dewaxing of mineral oils. Due to its relatively large utilizations, the quantities of hexane emitted into the atmosphere can be significant, being therefore necessary to control the emissions by different techniques, particularly by adsorption. Activated carbon adsorption has been considered to be one of the promising methods for controlling VOCs at low concentrations with potential to recover valuable vapors (Cheng et al, 2004; Ghiaci et al., 2004; Lillo-Rodenas et al., 2006; Tsai et al., 2008). However, it has been recognized that activated carbon adsorption always encounters some problems such as combustion, pore blocking, inefficiently desorption of high-boiling solvents and hygroscopicity (Guillemot et al., 2008; Li et al., 2009; Liu et al., 2008). Therefore, it is important to develop new adsorbent materials to separate and recover VOCs from polluted air streams. In the past few decades, polymeric adsorbent has emerged as a potential alternative to activated carbon for removing the organic pollutants from aqueous solution due to its controllable pore structure, stable physical, chemical properties as well as regenerability on site. More recently, hypercrosslinked polymeric resin (Tsyurupa and Davankov, 2006), which is produced by crosslinking polymers of macroporous resin in a good solvent and represent a class of predominantly microporous organic materials with high surface areas and high micropore volume, has gained increasing interest. Now hypercrosslinked polymeric resin produced by many manufactures worldwide is finding increased

application as sorbents for separation or analytical purposes and water pollution control (Baya et al., 2000; Chang et al., 2008; Long et al., 2009; Streat and Sweetland, 1998). However, it appears that the only published work proposing the removing of VOCs from gas stream onto hypercrosslinked polymeric resin is the paper of Liu et al. (2008). The objective of the present work is to investigate the adsorption potential of two hypercrosslinked polymeric resins: MN 202 and MN 250 comparatively with the adsorption potential of a granular activated carbon: AC 20 for removing the nhexane vapors from gaseous flux at different concentrations and at different adsorption temperatures. The experimental results were fitted to the Freundlich, Langmuir and Dubinin-Raduchkevich isotherms and the characteristics parameters of each model were obtained to describe equilibrium isotherms. 2. Experimental 2.1. Materials In this study two commercial HypersolMacronetTM hypercrosslinked polymers (MN 202 and MN 250) and a granular activated carbon AC 20 (Purolite) were used. Both polymers consist of macroporous polystyrene crosslinked with divinylbenzene without functional groups. The principle of Hypersol-Macronet resins is that the porosity is not introduced during polymerization, but during a post polymerization process in which the polymer is hypercrosslinked in a swollen state and results two special properties: a very high surface area, comparable with activated carbon and swelling even by liquids and gases that do not normally solvate the polymeric matrix. The polymers from class MN -200 tend to be hydrophobic and may be considered for the removal of more hydrophobic species. The physicochemical characteristics of MN 202, MN 250 and AC 20 are presented in Table 1 (Purolite Technical Bulletin, 1998).

Table 1. The physico-chemical characteristics of adsorbents (MN 202, MN 250 and AC 20) Characteristics Structure Physical Appearance Whole Bead Content Shipping weight, g/L Screen size range Bead size range Volatile moisture Specific Gravity, g/mL pH range Surface area (m2/g) (BET) Pore volume (mL/g) d50, A meso and macroporores d50, A micropores Moisture, % MN 202 MN 250 Crosslinked polystyrene Opaque Spherical beads > 90% 700 670-700 16-50 mesh < 5% greater than 1.2 mm. < 1% smaller than 0.3 mm cca. 55 % 1.04 0-14 931 m2/g 985 m2/g 1-1.1 0.6-0.8 850-950 300-400 15 14 57-62 AC 20 Bituminous granular carbon Black Spherical beads 0.4 1.4 mm 900-1000 m2/g max. 2

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All adsorbents were supplied from Purolite International Limited, Country offices of Purolite Corporation in Bucharest, Romania. The model pollutant studied in this work is nhexane (99.9%) purchased from Aldrich and used in without further purification. The physical properties of n-hexane are presented in Table 2. 2.2. Apparatus The experimental set-up used in the adsorption study is presented in Fig. 1. It is composed of three parts: first part is the vapor generation system, the second part is the adsorption system connected with the analytical equipment. Synthetic air, used as carrier gas, was initially passed through a gas purifier and a gas drier to remove any humidity and contaminants. Then, the main stream is divided in two lines; one is introduced into the n-hexane saturator, maintained at a controlled temperature (20C), to obtain a saturated air stream. The VOC saturated stream was then mixed with the second line, to obtain the desired n-hexane concentration. Mass flow controllers were used to control the gas flow rates into the adsorption system. The adsorption process takes place in a quartz column (1 cm x 20 cm) in which the adsorbents were introduced.

The temperature of adsorption process was controlled and measured by a thermocouple placed as close to adsorber column as possible. The concentration of n-hexane in the air stream, before and after the adsorption column, was measured by using a gas chromatograph (Carlo Erba 4200 Series) equipped with a six-way valve. The GC is equipped also with a column with 10% DC-200 Chromosorb PNAW, a flame ionization detector (FID) and an integrator. The GC was operated at an injection temperature of 170C, a detector temperature of 170C and an oven temperature of 110C. Nitrogen was used as a carrier gas. Also, an analytical balance was used to record the weight of adsorbents before and after adsorption. 2.3. Methodology Prior to each test, the desired air flow rate was established. The adsorbent sample was pretreated in an oven at 120C for 24 h for removing the moisture and other contaminants that were physically adsorbed during storage. Then, the adsorbents were cooled to room temperature and introduced in the adsorption column to make a layer with 1 cm height. The adsorption column with the dry sample was weighted (0.2 g of MN 202/MN 250 and 0.3 g of AC 20).

Table 2. Physical properties of n-hexane Characteristics Class Molecular formula Molecular weight (g/mol) Heat of vaporization (kJ/mol) Dipole moment (x 10-29 C m) Molecular diameter (nm) Molecular lenght (nm) Bulk liquid density at 25C (cm3/g) Saturation vapour pressure at 25C (atm) Boling point (C) Value Alkane C6H14 86.18 31.9 0 0.265 0.681 0.66 0.198 68.8

Fig. 1. A schematic diagram of adsorption process 1 - air compressor, 2 - valve, 3 - silica tube, 4 - activated carbon tube, 5 drierite columns, 6 - VOC saturator, 7 - thermostat, 8 manometer, 9 - rotameter, 10 - absorber column, 11 - adsorbent layer, 12 heating jacket, 13 - gas-chromatograph, 14 - recorder, 15 N2 tank, 16 H2 tank, 17 pressure reducer.

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Desired concentrations of adsorbates were obtained by adjusting the flow rate through the saturator vessel, containing liquid n-hexane. Vapors of know concentration were then continuously passed through the adsorption column. The sample sorbed the vapors and gained mass until the equilibrium was achieved and the n-hexane concentration become constant and stable. The gain in sample mass was determined by weighting the column with the adsorbent again and the n-hexane concentration was determined by GC. The vapor concentration was then changed by readjusting the air flow rate in the nhexane vessel to obtain another data point. The flow rate of the gaseous flux with n-hexane vapor air mixture entering at the adsorption column was controlled at 130 ml/min. The experiments were performed at ambient pressure at 30, 40 and 50C and at vapor concentration ranging from 2100 to 4500 ppm. 3. Results and discussion 3.1. Adsorption equilibrium

The hypercrosslinked polymeric resin MN 250 exhibited the higher adsorption capacities, in all studied conditions, while the adsorption capacities for MN 202 and AC 20 were similar (MN 250>AC 20>MN 202).
160 150
q e (m g/g)

(a)

140 130 120 110 100 1000

30C

2000
40C 50C

3000
Ce (ppm)

4000

5000

(b)

190 180
q e (m g /g )

170 160 150 140 130 1000

30C

The adsorption equilibrium data for n-hexane on the hypercrosslinked polymeric resins MN 202 and MN 250 as well as on the activated carbon AC 20 are shown in Fig. 2. Measurements were performed at 30C, 40C and 50C and the concentrations of nhexane in the gaseous flux were 2100, 3200 and 4500 ppm. The adsorption isotherms of n-hexane at equilibrium were found to be close to type I according to the IUPAC classification, indicating that the adsorption is mainly produced in the micropores. The adsorption capacity for n-hexane (qe), at 30C, ranged from 142 to 157 mg/g on MN 202, from 178 to 187 mg/g on MN 250 and from 160 to 164 mg/g on AC 20 (Table 3). When the adsorption temperature increased to 40C, the adsorption capacity was reduced from that at 30C as follows: 912% for MN 202, 13-18% for MN 250 and 7-9% for AC 20; and for a temperature of 50C: 15-20% for MN 202, 19-22% for MN 250 and 13-14% for AC 20 comparatively with adsorption capacities at 30C. It was observed that while increasing the adsorption temperature, the adsorption capacity is reduced and this effect is more pronounced at low concentration that at high concentration.

2000
40C 50C

3000
Ce (ppm)

4000

5000

(c)

170 165 160 155 150 145 140 135 130 1000
30C

qe (m g/g)

2000
40C 50C

3000
Ce (ppm )

4000

5000

Fig. 2. (a )- (c) Equilibrium adsorption isotherms of nhexane vapors from gaseous flux on: (a) MN 202, (b) MN 250 and (c) AC 20 at 30C, 40C and 50C

Table 3. Adsorption capacities of n-hexane (mg/g) on different adsorbents and at different temperatures Concentration (ppm) 2100 3200 4500 MN 202 40C 124 138 143 MN 250 40C 146 156 164 AC 20 40C 145 150 152

30C 142 154 157

50C 112 126 131

30C 178 184 187

50C 138 147 152

30C 160 162 164

50C 137 141 142

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Adsorption of n-hexane vapor onto non-functionalized hypercrosslinked polymers

3.2. Isotherm modeling The equilibrium sorption isotherm is fundamentally very crucial in design of sorption process. The equilibrium sorption is usually described by an isotherm equation characterized by certain constants which values express the surface properties and affinity of the adsorbent. The equilibrium relationships between adsorbent and adsorbate are described by sorption isotherms at a fixed temperature at equilibrium. In this study, for investigating the sorption isotherm, three different isotherm models were examined and in each case the isotherm constants were determined. These included the Freundlich, the Langmuir and the DubininRadushkevich adsorption isotherms. The Freundlich equation is one of the earliest empirical equations for describing adsorption equilibrium isotherms. This equation assumes that the adsorbent surface is heterogeneous (the adsorption energy is different for different adsorption sites), the adsorptions sites with the same adsorption energy are grouped together, the groups of different adsorption sites are independent of each other, only one molecule adsorbs onto one adsorption site, and adsorption occurs at a constant temperature (Agnihotri et al., 2005, Li et al., 2009). The Freundlich adsorption isotherm has the form of:

log qe
2.2 2.18 2.16 2.14 2.12 2.10 2.08 2.06 3.30 3.35 3.40 3.45

(a)

3.50 log Ce

3.55

3.60

3.65

3.70

T=30C

T=40C

T=50C

Freundlich

log qe
2.28 2.26 2.24 2.22 2.20 2.18 2.16 2.14 3.30 3.35 3.40 3.45

(b)

3.50 log Ce

3.55

3.60

3.65

3.70

T=30C

T=40C

T=50C

Freundlich

Liniar (T=40C)

log qe
2.22 2.21 2.20

(c)

q = KC 1 / n

(1)

where q is the adsorption capacity at equilibrium (mg/g), C is the equilibrium gas phase concentration of the adsorbate (ppm), and K and n are constants. The equation 1 can be rearranged in the linear form by taking the logarithm of both sides as (Ghiaci et al., 2004):

2.19 2.18 2.17 2.16 2.15 3.30 3.40 3.50 log Ce 3.60 3.70

log (q ) = log (K ) +

1 log (C ) n

T=30 C

T=40C

T=50 C

Freundlich

(2)
Fig. 3. (a) (c) Linearized Freundlich model for n-hexane adsorption onto: (a) MN 202, (b) MN 250 and (c) AC 20 at 30C, 40C and 50C

Freundlich constants K and n are generally temperature dependant; n is related to the affinity of the adsorbate to the adsorbent surface (the smaller the value of n, the stronger the attraction between adsorbate and adsorbent). The values of K and n can be calculated from the slop and intercept of the log(q) vs. log (C) curve for the experimental obtained data (eq. 2). These values are then used to calculate q for a given value of C from Eq. 1. Figs. 3(a)(c) show the linear Freundlich isotherms for the adsorption of n-hexane on MN 202, MN 250 and AC 20 respectively at 30C, 40C and 50C and Table 4 presents the Freundlich equations, the Freundlich constants K and n and correlation coefficients - R2 for all adsorbents at each temperatures. Based on the R2 values, the linear Freundlich model have a high level of conformity with the experimental data of n-hexane adsorption.

According to Table 4, the values of K for each adsorbents decrease with increasing temperature. The adsorption coefficient K is related to the affinity of the adsorbent for the adsorbate, and n is a function of the strength of adsorption. For fixed values of C and n, the larger value of K, the larger is the adsorption capacity, q. For fixed values of K and C, the smaller value of 1/n, the stronger is the adsorption affinity. The Freundlich constant n is also a measure of deviation from the linearity of the adsorption. If n = 1, the isotherms becomes linear in a normal plot. In this case, loading is proportional to concentration. This is typical of solubility, or Henrys law type sorption mechanism. Larges values of n reflect an isotherm that flattens out as concentration increases.

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Table 4. Freundlich constants and equation for n-hexane adsorption on MN 202, MN 250 and AC 20 Adsorbent MN 202 Temperature (C) 30 40 50 30 40 50 30 40 50 Freundlich equation log (qe) = 0.097 log (Ce) + 1.8308 log (qe) = 0.0989 log (Ce) + 1.7928 log (qe) = 0.1091 log (Ce) + 1.719 log (qe) = 0.0673 log (Ce) + 2.0264 log (qe) = 0.0762 log (Ce) + 1.974 log (qe) = 0.1154 log (Ce) + 1.7774 log (qe) = 0.0386 log (Ce) + 2.0742 log (qe) = 0.0473 log (Ce) + 2.03 log (qe) = 0.0675 log (Ce) + 1.9305 K 67.74 62.05 52.36 106.26 94.19 59.9 118.36 107.15 85.21 n 10.31 10.11 9.16 14.85 13.13 8.67 25.9 21.14 14.81 R2 0.9987 0.989 0.9981 0.998 0.9929 0.997 0.9998 0.9997 0.9997

MN 250

AC 20

This is typical of a non-homogenous surface area driven mechanism. In sorption process, this results in a favorable, self-sharpening breaktrough curve. Table 4 shows that n for all studied adsorbent is greater than 1, which is mean that the n-hexane vapors adsorb to surface sites of these adsorbents and the adsorption process of n-hexane vapors on MN 250, MN 202 and AC 20 adsorbents is favorable. The Langmuir equation has been widely applied to many sorption processes (Ghiaci et al., 2004). Langmuir equation is based on fundamental kinetic theory of adsorption onto a flat surface (Eq. 3). It proposes that adsorption equilibrium is balanced by a continual uptake of adsorbate molecules and a corresponding evaporation of molecules from the surface of the adsorbent. Langmuir equation assumes that the surface is homogeneous (the adsorption energy is constant for all sites), adsorbed molecule are immobile, each adsorption site can accommodate only one atom (single layer adsorption), and adsorption occurs at a constant temperature (Agnihotri et al., 2005; Li et al, 2009).
q bC = q m 1 + bC

Figs. 4(a)(c) depict the linear Langmuir isotherms for the adsorption of n-hexane on MN 202, MN 250 and AC 20 respectively at 30C, 40C and 50C and Table 5 presents the Langmuir equations, the maximum adsorption capacities - qm (mg/g), the Langmuir constants b and the coefficients of correlation - R2 for MN 250, MN 202 and AC 20 adsorbents at each temperatures studied.
1/q 0.0090 0.0085 0.0080 0.0075 0.0070 0.0065 0.0060 0.00020 0.00025
30C 40C (a)

0.00030
50C

0.00035
1/C Langmuir

0.00040

0.00045

0.00050

1/q 0.0075 0.0070 0.0065

(b)

(3)

0.0060 0.0055 0.0050 0.00020

where q is the adsorption capacity (mg/g) corresponding to adsorbate concentration C (ppm), qm is the maximum adsorption capacity (mg/g), (also, the capacity for the complete surface coverage by single layer of adsorbate molecules) and b is the Langmuir constant which is related to the activation energy of the adsorption site. Eq. 3 can be rearranged in the linear form also:
1 1 1 = + q q m bq m C

0.00025
30C 40C

0.00030
50C

0.00035
1/C

0.00040

0.00045

0.00050

Langmuir

1/q 0.0072 0.0070 0.0068 0.0066 0.0064 0.0062

(c)

(4)

0.006 0.0002

0.00025
30C

0.0003
40C

0.00035
1/C

0.0004

0.00045

0.0005

50C

Langmuir

The value for qm and b can be calculated from the slope and the intercept of the 1/q vs. 1/C plot of the experimentally obtained isotherm data (Eq. 4). These values are then used to calculate q for a given value for C from Eq 3.

Fig. 4. (a) (c) Linearized Langmuir model for n-hexane adsorption onto: (a) MN 202, (b) MN 250 and (c) AC 20 at 30C, 40C and 50C

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Adsorption of n-hexane vapor onto non-functionalized hypercrosslinked polymers

It can be seen from Table 5 that the Langmuir isotherm is well applicable to the adsorption data of n-hexane vapors for all adsorbents studied, indicating a prevailing mono-molecular layer physiosorption process because of the square of all correlation factors, R2 is greater than 0.99. According to Langmuir equation, the maximum adsorption capacity of n-hexane at 30C, 40C and 50C were 204.08, 196.08 and 172.42 mg/g respectively, all performed by MN 250 adsorbent. Also, this equation shows that MN 202 exhibits greater efficiency on adsorption of n-hexane that AC 20, excepting the results at 50C where AC 20 have the maximum adsorption capacity (161.29 mg/g) greater than MN 202 (147.05 mg/g). The increase of temperature reduced the adsorption capacity and, it was observed that, this effect is most pronounced for the polymeric adsorbents MN 250 and MN 202 than for activated carbon AC 20. The Dubinin-Radushkevich (DR) Equation is based on micropore filling mechanisms (the chemical potential is a function of amount adsorbed) as opposed to other equation that are based on concepts of surface coverage. The DubininRadushkevich adsorption isotherm has the following form (Eq.5) (Agnihotri et al., 2005, Li et al, 2009):

Figs. 5(a)(c) shows the linear DR isotherms for the adsorption of n-hexane on MN 202, MN 250 and AC 20 respectively at 30C, 40C and 50C and Table 6 presents the DR equations, the maximum volume of adsorbate per unit mass of adsorbent W0 (cm3/g), the adsorption characteristic energies of adsorbates on adsorbents E0 (kJ/mole) as well as the coefficients of correlation - R2 for all adsorbents studied at each temperatures.
ln W (a)

-1.4 -1.45100 -1.5 -1.55 -1.6 -1.65 -1.7 -1.75

A^2 30 C 40 C 50 C DR

105

110

115

120

125

130

135

ln W

(b) 105 110 115 120 125 130 135

-1.2 100 -1.25 -1.3 -1.35

A W = W0 exp E0

(5)

-1.4 -1.45 -1.5 -1.55

A^2

where W is the volume of adsorbate per unit mass of adsorbent (cm3/g); W0 is the limiting pore volume of adsorption (volume of micropores) per unit mass of adsorbent (cm3/g); is the similarity coefficient which is a unitless constant equal to the ratio of the adsorption potentials for the adsorbate of interest and a reference adsorbate (e.g., benzene); E0 is the characteristics adsorption energy of the reference adsorbate; A is the differential molar work needed to transport one mole of the adsorbate to the surface of an infinitely large adsorbent (kJ/mole); A can be calculate with Eq. 6:

30 C

40 C

50 C

DR

ln W

-1.38 -1.40100 -1.42 -1.44 -1.46 -1.48 -1.5 -1.52

(c)

105

110

115

120

125

130

135

p A = G = RT ln 0 p

(6)

-1.54
A^2

where G is the Gibbs free energy; R is the ideal gas law constant (J/mol K); T is the absolute temperature (K). Eq. 5 can be rearranged in the linear form also (Eq.7):
1 ln W = ln W0 E 0 2 A
2

30 C

40 C

50 C

DR

Fig. 5. (a) (c) Linearized Dubinin-Radushkevich (DR) model for n-hexane adsorption onto: (a) MN 202, (b) MN 250 and (c) AC 20 at 30C, 40C and 50C

(7)

The parameters E0 and W0 can be determinate from the slope and the intercept of the ln W vs. A2 curve for the experimentally obtained data (Eq. 7). These values are then used to calculate W for a given value of p/p0 from Eq. 5 (Tsai et al., 2008).

The DR isotherm appears to be the most adequate model to describe the adsorption of nhexane on these polymeric materials, in dynamic conditions. Like in precedent models, the maximum adsorption capacities decrease with the temperature increasing, and the greater adsorption capacity is presented for MN 250. According to the volume filling of micropore theory, the smaller E0, the easier it is for the adsorbates to adsorb onto the solid surface.

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Table 5. Langmuir constants and equation for n-hexane adsorption on MN 202, MN 250 and AC 20 Adsorbent MN 202 Temperature (C) 30 40 50 30 40 50 30 40 50 Langmuir equation 1/q = 3.0588(1/C) + 0.0058 1/q = 3.1242(1/C) + 0.0061 1/q = 3.4702(1/C) + 0.0068 1/q = 1.1105(1/C) + 0.0049 1/q = 2.0604(1/C) + 0.0051 1/q = 2.4580(1/C) + 0.0058 1/q = 0.7055(1/C) + 0.0059 1/q = 0.9974(1/C) + 0.0061 1/q = 2.0272(1/C) + 0.0062 qm (mg/g) 172.42 163.93 147.05 204.08 196.08 172.42 169.49 163.93 161.29 b (ppm-1) 0.0019 0.0019 0.0019 0.0044 0.0025 0.0024 0.0084 0.0061 0.0031 R2 0.996 0.9964 0.9982 0.9977 0.9999 0.9979 0.9921 0.9998 0.9957

MN 250

AC 20

Table 6. Dubinin-Radushkevich constants and equation for n-hexane adsorption on MN 202, MN 250 and AC 20 Adsorbent MN 202 Temperature (C) 30 40 50 30 40 50 30 40 50 DR equation ln W = - 0.0026 A2 1.1912 ln W = - 0.0027 A2 1.2577 ln W = - 0.0029 A2 1.3133 ln W = - 0.0019 A2 1.065 ln W = - 0.0021 A2 1.0951 ln W = - 0.0031 A2 1.1082 ln W = - 0.0010 A2 1.2852 ln W = - 0.0013 A2 1.2892 ln W = - 0.0018 A2 1.2917 Wo (cm3/g) 0.304 0.284 0.269 0.345 0.335 0.331 0.278 0.276 0.274 Eo (kJ/mol) 19.62 19.24 18.57 22.95 21.83 17.97 31.62 27.74 23.58 R2 0.9996 0.9998 0.998 0.9991 0.9993 1 1 0.999 0.9991

MN 250

AC 20

The values for the characteristic adsorption energy (E0) were 18.57 19.62 kJ/mole for MN 202, 17.97 22.95 kJ/mole for MN 250 and 23.58 31.62 kJ/mole for AC 20. MN 250 and MN 202 have lower values for the adsorption characteristic energy, as compared to AC 20, and this may be attributed to the hydrophobic character of these hypercrosslinked polymeric resins. 4. Conclusions Adsorption equilibrium of n-hexane vapors from gas phase onto hypercrosslinked polymeric resins (Hypersol-MacronetTM MN 202 and MN 250) and granular activated carbon AC 20 was investigated. It was observed that the MN 250 adsorbent exhibits the greater adsorption capacity for n-hexane, in our experimental conditions, while the adsorption capacities of MN 202 and AC 20 are almost identical. The adsorption capacities of n-hexane for each adsorbent decreased with the increasing adsorption temperature. It was observed that, the influence of temperature on the adsorption capacities is most pronounced in the case of MN 250 and MN 202 adsorbents that in the case of granular activated carbon AC 20. The experimental results were analyzed by using the Freundlich, Langmuir and DubininRadushkevich (DR) equations. According to the values of the correlation coefficients (R2), the better fitting results were achieved by using the DR model isotherm, followed by Langmuir and Freundlich models.

The results of this study indicate that the hypercrosslinked polymeric adsorbents MN 202 and MN 250 could be successfully used for n-hexane adsorption from polluted air streams.
Acknowledgement This work was supported by the Program Resurse Umane, Grant TD_196, Contract No. 279/2007, in the frame of the National Program for Research, Development and Innovation II Ministry of Education and Research, Romania. The authors wish to thanks to Purolite Company for supporting this work with adsorbents supplying.

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