Adsorption and Ozonation Kinetic Model for Phenolic Wastewater Treatment

CATALYSIS, KINETICS AND REACTORS Chinese Journal of Chemical Engineering, 19(1) 76ü82 (2011)

Adsorption and Ozonation Kinetic Model for Phenolic Wastewater Treatment* Wongsarivej Pratarn1,**, Tongprem Pornsiri1, Swasdisevi Thanit2, Charinpanitkul Tawatchai3 and Tanthapanichakoon Wiwut3 1

National Nanotechnology Center, Thailand Science Park, Klong Luang, Pathumthani 12120, Thailand School of Energy, Environment and Materials, King Mongkut’s University of Technology Thonburi, 126 Pracha u-tid Rd., Bangkok 10140, Thailand 3 Center of Excellence in Particle Technology, Faculty of Engineering, Chulalongkorn University, Payathai Rd., Wangmai, Pathumwan, Bangkok 10330, Thailand 2

Abstract A three phase fluidized bed reactor was used to investigate the combined effect of adsorption and oxidation for phenolic wastewater treatment. Aqueous solutions containing 10 mg·L1 of phenol and ozone were continuously fed co-currently as upward flow into the reactor at constant flow rate of 2 and 1 L·min1, respectively. The phenolic treatment results in seven cases were compared: (a) O3 only, (b) fresh granular activated carbon (GAC), (c) 1st reused GAC, (d) 2nd reused GAC, (e) fresh GAC enhanced with O3, (f) 1st reused GAC enhanced with O3, and (g) 2nd reused GAC enhanced with O3. The phenolic wastewater was re-circulated through the reactor and its concentration was measured with respect to time. The experimental results revealed that the phenolic degradation using GAC enhanced with O3 provided the best result. The effect of adsorption by activated carbon was stronger than the effect of oxidation by ozone. Fresh GAC could adsorb phenol better than reused GAC. All cases of adsorption on GAC followed the Langmuir isotherm and displayed pseudo second order adsorption kinetics. Finally, a differential equation for the fluidized bed reactor model was used to describe the phenol concentration with respect to time for GAC enhanced with O3. The calculated results agree reasonably well with the experimental results. Keywords adsorption, ozonation, kinetic model, phenol, wastewater

1

INTRODUCTION

Activated carbon, also called activated charcoal or “activated coal”, is a form of carbon that is made extremely porous and possesses a very large surface area available for adsorption and chemical reaction. Granular activated carbon (GAC) has relatively larger particle sizes than powdered activated carbon and consequently has a smaller specific external surface. Diffusion through the pores of the adsorbate is thus an important factor. The GAC is nevertheless effective for adsorption of gases and vapors as their rates of diffusion are faster than those of liquids. Granulated carbons are also used for treating water and wastewater to reduce pressure drop and elutriation loss [1]. Ozone (O3) is a triatomic molecule, consisting of three oxygen atoms. It is an allotrope of oxygen that is much less stable than the diatomic allotrope (O2). Ozone in the lower atmosphere is an air pollutant with harmful effects on the respiratory systems of animals. Exposure of 0.1×106 to 1×106 produces headaches, burning eyes, and irritation to the respiratory passages [2]. Even low concentrations of ozone in the air could be destructive to various organic materials such as latex, plastics, and lungs. Ozone could be generated by several methods, for example, corona discharge, ultraviolet light and cold plasma [3]. Industrially, ozone is used to chemically attack contaminants in water such as iron, arsenic, hydrogen sulfide, nitrites

and complex organics, often lumped together as color. In various industrial processes, phenol is one of the important starting or intermediate materials. Phenol is known to be carcinogenic and possesses high stability and high toxicity. It has been declared to be hazardous pollutant even at very low concentration [4]. It can damage the skin and other tissues of the human and animals. When digested, phenol-containing liquids could lead to liver damage, dark urine and irregular heart beats. Therefore, the treatment of phenolic wastewater is of considerable importance in environmental protection. Many technologies have been attempted for treating phenolic wastewater, for example, biological treatment [5], chemical precipitation or oxidation [6], ion exchange [7], and adsorption [8]. However, there are few processes to deal with this highly toxic wastewater with reasonable costs. The degradation of aqueous phenol by simultaneous use of ozone and activated carbon or zeolite offers an environmentally friendly alternative of phenolic treatment [913]. In this research, the removal of phenol by adsorption on GAC without and enhanced with ozone is investigated using a laboratory scale three phase fluidized bed reactor. The adsorption isotherm and kinetics of GAC are examined and modeled. A differential equation to describe the phenol concentration with respect to time for the case of GAC enhanced with O3 is derived and examined.

Received 2010-06-02, accepted 2010-12-27. * Supported by the National Nanotechnology Center (NANOTEC) (601003) and the National Science and Technology Development Agency (NSTDA). ** To whom correspondence should be addressed. E-mail: [email protected]

Chin. J. Chem. Eng., Vol. 19, No. 1, February 2011

2

EXPERIMENTAL

2.1 Activated carbon preparation The test GAC made from coconut shell was purchased from Carbokarn (Thailand) Co., Ltd. The GAC was sieved to select the size range of 0.42.0 mm particle diameter. The classified GAC was heated and held at 473 K for 4 h to eliminate its moisture and volatile impurities. 2.2

Characterization

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collected from the effluent stream with respect to time. The adsorption and oxidation of activated carbon and ozone were investigated in seven cases: (a) O3 only, (b) fresh GAC, (c) 1st reused GAC, (d) 2nd reused GAC, (e) fresh GAC enhanced with O3, (f) 1st reused GAC enhanced with O3, and (g) 2nd reused GAC enhanced with O3. Their phenolic elimination performance was analyzed and evaluated. 2.4

Chemical analysis

Following the Brunauer-Emmett-Teller (BET) adsorption method, the specific surface area and porosity of the activated carbon were measured via N2 adsorption-desorption isotherms. Test materials were measured at 77 K using an automatic adsorption apparatus (BELSORP 28, BEL Japan Inc.). The morphological structure of the activated carbon was characterized by scanning electron microscope (SEM, Hitachi S-3400N).

The progress of the removal was followed by periodically taking the liquid samples from the reactor for immediate analysis after filtration through 0.45 Pm nylon filter. Phenol was identified and quantified by high performance liquid chromatography (HPLC, Shimadzu LC-20A Series) with a diode array detector at wavelengths of 210 and 254 nm. A 5 Pm column of C18 (Inertsil ODS-3, 25 cm long, 4.6 mm diameter) was used as stationary phase and a mixture of 4 mmol·L1 aqueous sulphuric and acetonitrile (volume ratio of 4Ή1) was used as mobile phase at 1 ml·min1.

2.3 Apparatus and procedure

3

A laboratory scale three phase fluidized bed reactor was used as the adsorption and oxidation system to improve mixing and homogeneity. Its schematic diagram is shown in Fig. 1. The reactor with an effective volume of 272 ml was made from transparent acrylic that allowed the observation of the phenomena inside. The outside diameter and height of the reactor were 40 and 300 mm, respectively. The aqueous solution containing 10 mg·L1 of phenol was treated and 256.8 g·h1 of O3 was used as oxidizing agent. A constant flow rate of 1 L·min1 of the solution and 2 L·min1 of O3 were continuously fed co-currently into the reactor as upward flow. Then, the liquid effluent stream was recycled to the hold-up tank. 6 L of phenolic wastewater containing in the tank of 15 L was treated with activated carbon of 5 g. The solution temperature in the tank was monitored and controlled at 303 K using a thermocouple and a cooler. The samples were

RESULTS AND DISCUSSION

3.1

Characterization of activated carbon

The pore size distribution of GAC measured with the MP-Plot method was found to be essentially microporous with a modal peak of 0.6 nm, and the BET surface area and total pore volume of GAC were 1154 m2·g1 and 0.49 cm3·g1, respectively. To understand the morphology of GAC surface, its image was obtained with scanning electron microscope (see Fig. 2) to reveal the high surface area structure of GAC. The abundant micropores provide superb condition for the adsorbed material to interact with the ozone at high concentration.

Figure 2

3.2 Figure 1 Schematic diagram of experimental apparatus 1ühold-up tank; 2üliquid pump; 3üball valve; 4üliquid flow meter; 5üair flow meter; 6üozone generator; 7üair pump; 8ü three phase fluidized bed reactor

Scanning electron microscope image of GAC

Adsorption isotherms

The capacity of virgin activated carbon to adsorb aqueous phenol was determined by measuring the adsorption isotherm at 298 K, as shown in Fig. 3. The

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The Langmuir and Freundlich parameters for the adsorption of phenol onto activated carbon are listed in Table 1. This table and Fig. 3 show conclusively that Langmuir isotherm provides a significantly higher regression coefficient R2 than Freundlich isotherm. This means that the surface of GAC is made up of homogeneous adsorption patches, which is in good agreement with other reports [2123]. Figure 3 Equilibrium adsorption isotherm of fresh activated carbon fitted with Langmuir and Freundlich adsorption isotherm ƻ fresh GAC; Langmuir isotherm; Freundlich isotherm

analysis of the isotherm data is important to develop an equation that accurately represents the equilibrium and can be used for design purpose. In this study, two commonly used equilibrium models are selected to describe the adsorption data, namely the Langmuir and the Freundlich isotherm equations [1420]. The Langmuir theory assumes a homogeneous monolayer adsorption within the adsorbent. The linear form of the Langmuir isotherm equation is represented as qmax K L Ce qe (1) 1  K L Ce

After rearrangement Eq. (1) becomes Ce 1 1 Ce  qe qmax K L qmax

K FCe1/ n

Adsorption isotherm constants for the phenol onto virgin activated carbon at 30 qC Langmuir model

Freundlich model

Adsorbent

qmax /mg·g1

KL /L·mg1

R2

n

KF /L·g1

R2

fresh GAC

232.558

0.149

0.997

3.504

50.096

0.974

The GAC adsorption of phenol as a function of time is shown in Fig. 4. Obviously fresh GAC presents slightly faster adsorption than 1st reused GAC though their final capacities are essentially the same. This implies that the regeneration is complete though some of the micropores become slightly narrower. Similarly, 1st reused GAC presents slightly faster adsorption than 2nd reused GAC. After 360 min, the adsorption equilibrium is reached. The adsorption of both GAC and reused GAC follow the pseudo second t 1 t  . order kinetics, that is 2 qt ka 2 qe qe

(2)

where qe is the equilibrium phenolic concentration on the adsorbent (mg·g1), Ce the equilibrium concentration of phenol in the solution (mg·L1), qmax the maximum monolayer adsorption capacity of the adsorbent (mg·g1), and KL is the Langmuir isotherm constant (L·mg1) related to the free energy of adsorption. A plot of Ce/qe versus Ce for the adsorption of phenol onto the activated carbon gives a straight line of slope of 1/qmax and intercept of 1/qmaxKL. The Freundlich isotherm is an empirical equation assuming that the adsorption takes place on heterogeneous surfaces of solids and in multilayer sorption manner. The adsorption capacity is the adsorbed concentration of phenol at equilibrium. The linear form of Freundlich equation is qe

Table 1

(3)

After rearrangement Eq. (3) becomes 1 ln qe ln Ce  ln K F (4) n where KF (L·g1) and n are Freundlich adsorption isotherm constants indicative of the adsorption capacity and the degree of nonlinearity between solution concentration and adsorption, respectively. The plot of lnqe versus lnCe is employed to generate KF value from the intercept and n value from the slope.

Figure 4 GAC adsorption of phenol as a function of time ƻ fresh GAC;Ƹ1st reused GAC;ƶ2nd reused GAC

3.3

Adsorption kinetics

Two kinetic models, the pseudo first order and pseudo second order, were tested with the experimental data to elucidate the adsorption phenomenon with the air fed co-currently instead ozone. In the case of the first order rate equation for GAC, with 1st reused GAC and 2nd reused GAC, the values of ka1 and qe were calculated from the slope and intercept of the plot of lg(qeqt) versus t (see Fig. 5) and summarized in Table 2. It is found that the correlation coefficients for the pseudo first order model are significantly lower than those of the pseudo second order model. Coupled with the fact that the lines in Fig. 5 are not straight, it conclusively shows that the adsorption process does not follow the first order kinetics.

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Chin. J. Chem. Eng., Vol. 19, No. 1, February 2011 Table 2

Experimental and calculated adsorption ability and rate constant of GAC with 1st reused GAC and 2nd reused GAC

Sample

Pseudo-first order

Pseudo-second order

qe (exp)/mg·g1

qe (cal)/mg·g1

kal (exp)/mg·g1·min1

R2

qe (cal)/mg·g1

ka2/g·mg1·min1

R2

fresh GAC

11.90

7.36

0.0157

0.9551

12.69

0.0038

0.9994

1st reused GAC

11.89

7.76

0.0150

0.9497

12.94

0.0029

0.9977

2nd reused GAC

11.86

8.19

0.0150

0.9635

13.00

0.0026

0.9976

Figure 5 Pseudo first order analysis for GAC with 1st reused GAC and 2nd reused GAC ƻ fresh GAC;Ƹ1st reused GAC;ƶ2nd reused GAC

In the case of the second order rate equation for GAC, with 1st reused GAC and 2nd reused GAC, the values of ka2 and qe were calculated from the plot of t/qt against t (see Fig. 6 and Table 2). The calculated qe values agree essentially with the experimental values. The correlation coefficients for the pseudo second order kinetic plots are very high, indicating that the adsorption kinetics of both GAC and reused GAC are the pseudo second order.

Figure 6 Pseudo second order analysis for GAC with 1st reused GAC and 2nd reused GAC ƻ fresh GAC;Ƹ1st reused GAC;ƶ2nd reused GAC

3.4

Ozonation kinetics

The transient of phenolic degradation with O3 only (ozone-rich air without GAC) was analyzed to determine the rate constant kr for pseudo first order kinetics. The rate constant was determined from the slope of ln(C/C0) vs. t by fitting the data at 0180 min, as shown in Fig. 7. Here C0 and C are the phenol concentration at the initial and at time t, respectively. The experimental results of the degradation of phenol solution reveals that the employment of O3 only gives an initial rate constant kr 0.0122 L·g1·min1 with R2 value of 0.9907. In this case the degradation of phenol follows the pseudo first order kinetics since the plot of ln(C/C0) vs. t presents a straight line.

Figure 7 The plot of ln(C/C0) vs. t for the reaction between phenol and ozone

3.5

The coupling between adsorption and ozonation

In three out of the seven experimental cases, the coupled adsorption and oxidation performance of GAC and ozone was investigated under the same experimental conditions. The three cases are (e) fresh GAC enhanced with O3, (f) 1st reused GAC enhanced with O3, and (g) 2nd reused GAC enhanced with O3. The results for the seven cases are presented in Fig. 8. Each of the shown data points is the average value of triplicate data. As expected, using only O3 is the worst for phenol degradation. When employing only GAC and air, the degradation performance is significantly better. In the cases of GAC enhanced with O3, the performance is further improved significantly. In the best case, complete degradation of phenol is achieved within 75 min. In summary, the removal effect of adsorption by GAC is stronger than that of oxidation by ozone. GAC adsorbs phenolic compounds in aqueous solutions until it reaches equilibrium. Interestingly, when coupling the effect of adsorption together with the effect of ozonation, phenol can be eliminated faster than in the four previous cases, either O3 or GAC only.

Figure 8 Phenol concentration as a function of time for fresh and reused GAC without and enhanced with O3 × O3 only;ƻfresh GAC-air;Ƹ1st reused GAC-air;ƶ2nd reused GAC-air;ƽfresh GAC-O3;Ʒ1st reused GAC-O3;Ƶ2nd reused GAC-O3

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In Fig. 8, the phenol adsorption of GAC in the three cases without ozone, fresh GAC and 1st reused GAC is the fastest and second fastest, respectively. This is consistent with the kinetic results shown in Fig. 4. Similarly, the phenol elimination in the three cases of GAC enhanced with O3, fresh GAC enhanced with O3 and 1st reused GAC enhanced with O3, is the best and second best, respectively. However, in actual wastewater treatment, using fresh activated carbon in each batch is economically impractical. The synergistic effect of adsorption with GAC and ozonation is an attractive alternative. Fortunately, the employment of used GAC with or without ozone shows small difference in adsorption rates after two regenerations. 3.6

Adsorption and ozonation kinetics

The ozone oxidation data were analyzed with the following second order rate equation for irreversible bimolecular reaction: dC rA  A kr CA CB (5) dt where kr is reaction rate constant, CA and CB are phenol and ozone concentrations, respectively. In our experiments, the concentration of ozone was replenished continuously and was essentially constant, so the rate equation can be reduced to first-order. dC rA  A kr CA (6) dt With separation of variables and integration of both sides, Eq. (6) becomes C  ln A kr t (7) CA0

where CA0 is the initial concentration of phenol. The adsorption data could be analyzed with either pseudo first order or pseudo second order kinetics: kt lg  qe  qt lg qe  a (8) 2.303 t qt

1 t  2 ka 2 qe qe

(9)

where qe and qt are adsorption ability at equilibrium and at time t (mg·g1) respectively, ka1 and ka2 are the first and second order adsorption rate constants, respectively. Our conclusion in Section 3.3 indicates a pseudo second order kinetics. Differentiation of both sides of Eq. (9) gives dqt 2 ka 2  qe  qt (10) dt Based on the assumptions of complete mixing in the fluidized bed and simultaneous adsorption and ozonation in the reactor, the mass balance equation for phenol in the three phase fluidized bed reactor can be

written as dqt dC V A (11) dt dt where mc is catalyst loading and V is liquid volume in the reactor. Substitution of Eqs. (6) and (10) into Eq. (11) yields dC 2 mc ka 2  qe  qt  V A  mc kr CA 0 (12) dt To integrate this equation, it is first written as an ordinary differential equation as follows M  t , CA ˜ dt  N  t , CA ˜ dCA 0 (13) rA mc

mc

More specifically, ª m k  q  q 2  m k C º ˜ dt  V ˜ dC t c r A¼ A ¬ c a2 e where M  t , CA

and

0 (14)

mc ka 2  qe  qt  mc kr CA

(15)

N  t , CA V

(16)

2

It should be noted that wM wN mc kr z wCA wt

0

(17)

Eq. (12) is not an exact ordinary differential equation, but it becomes an ODE after multiplication by an integrating factor, ȝ, ª § wM wN · 1 º  P exp « ³ ¨ ¸ ˜ dt » ¬ © wCA wt ¹ N ¼ § mk · §m k · exp ¨ ³ c r dt ¸ exp ¨ c r t ¸ © V ¹ © V ¹ Then Eq. (12) becomes dª § m k ·º V «CA exp ¨ c r t ¸ » dt ¬ © V ¹¼ §m k · 2 mc ka 2  qe  qt exp ¨ c r t ¸ © V ¹ The integration of Eq. (19) gives 2 §m k · §m k VCA exp ¨ c r t ¸ mc ka 2 ³  qe  qt exp ¨ c r © V ¹ © V

and Eq. (10) can be integrated to yield 1 1  ka 2 t qe  qt qe

or

qe  qt

qe 1  qe ka 2 t

(18)

(19) · t ¸ dt ¹ (20)

(21) (22)

Substitution of Eqs. (21) and (22) in Eq. (20) gives CA

m k q2 § mk  c a 2 e exp ¨  c r V © V

§m k · exp ¨ c r t ¸ · © V ¹ dt (23) t¸³ ¹ 1  qe ka 2 t 2

Chin. J. Chem. Eng., Vol. 19, No. 1, February 2011

Since the integral in Eq. (23) can not be integrated analytically, it is integrated using Wolfram Mathematica Software. To obtain some approximate analytical solution, the following indefinite integral is utilized §m k · exp ¨ c r t ¸ © V ¹ ³ 1  q k t 2 dt e a2

§ km exp ¨  r c © ka 2 qeV

· ¸˜ ¹

ª kr mc  ka 2 qe t  1 º °­ ®kr mc  ka 2 qe t  1 ˜ Ei « » ka 2 qeV °¯ ¬ ¼ ª k m  k q t  1 º ½° ka 2 qeV exp « r c a 2 e »¾ ka 2 qeV ¬ ¼ °¿ ª¬ ka22 qe2  ka 2 qeVt  V º¼  Const

(24)

Application of the initial condition CA CA0 at t 0 allows the evaluation of the Const term. Let us evaluate the complex exponential ª k m  k q t  1 º integral term, Ei « r c a 2 e » , by setting z ka 2 qeV ¬ ¼ kr mc  ka 2 qe t  1 and making use of the Puiseux seka 2 qeV ries of Ei(z) along the positive real axis, Ei ( z ) J  ln z  z 

1 2 1 3 z  z  4 18

1 4 1 5 z  z  ˜˜˜ (25) 96 600 where Ȗ is Euler gamma constant, Ȗ 0.577216···. Substitution of Eqs. (24) and (25) in Eq. (23) gives the phenol concentration CA with respect to time t analytically as an infinite series. Figure 9 shows the aqueous phenol concentration as a function of time for the three cases of GAC enhanced with O3. The comparison shows that the cal-

81

used to predict the phenol concentration with respect to time and to design a three phase fluidized bed reactor for wastewater treatment. 4

CONCLUSIONS

Removal of phenol in a laboratory scale three phase fluidized bed reactor with activated carbon either without or enhanced with ozone was examined experimentally and theoretically. Phenolic degradation using only O3 gave the worst result among the seven cases while using the coupling effect of GAC and O3 provided the best result. As expected, the phenol removal performance of fresh and 1st reused GAC turned out best and second best, respectively. This holds true for the cases of GAC without and GAC enhanced with ozone. The oxidation of phenol in the case of only O3 followed pseudo first order kinetics. Adsorption of phenol in all cases of GAC followed Langmuir isotherm and pseudo second order kinetics. Finally, the derived differential equations and their solutions for the three phase fluidized bed reactor yielded predicted results that agreed reasonably with the corresponding experimental results. NOMENCLATURE C CA CB Ce Ei KF KL ka1 ka2 kr mc n qe qmax qt rA t V z Ȗ ȝ

concentration, mg·L1 phenol concentration, mg·L1 ozone concentration, mg·L1 concentration of phenol in the solution, mg·L1 exponential integral Freundlich isotherm constants, L·g1 Langmuir isotherm constant, L·mg1 first order adsorption rate constant, mg·g1·min1 second order adsorption rate constant, g·mg1·min1 first order apparent kinetic rate constant, L·g1·min1 catalyst loading, g degree of nonlinearity between solution concentration and adsorption adsorption ability at equilibrium, mg·g1 maximum monolayer adsorption capacity of adsorbent, mg·g1 adsorption ability at time t, mg·g1 oxidation reaction rate of phenol, mg·g1·min1 time, min liquid volume, L mathematical term Euler gamma constant integrating factor

A B r 0

phenol ozone reaction initial condition

Subscripts

Figure 9 Comparison between the calculated CA (line) and experimental CA (dot) for GAC enhanced with O3 exp.:ƻfresh GAC-O3;Ƹ1st reused GAC-O3;ƶ2nd reused GAC-O3; cal.: fresh GAC-O3; 1st reused GAC-O3; 2nd reused GAC-O3

culated values of CA from the differential equations agree reasonably well with the corresponding experimental results. Therefore, both the computational results and the approximate analytical solution can be

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