Process Biochemistry 45 (2010) 3038

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Process Biochemistry
journal homepage: www.elsevier.com/locate/procbio

Dynamic transport and reaction model for azo dye removal in a UAFB reactor
lez-Gutie rrez a,1, Hugo Jime nez-Islas b, Eleazar M. Escamilla-Silva b,* Linda V. Gonza
a b

n y Desarrollo Tecnolo gico en Electroqumica, Parque Tecnolo gico Quere taro Sanfandila, 76703 Sanfandila, Pedro Escobedo, Qro., Mexico Centro de Investigacio gico de Celaya, Departamento de Ingeniera Qumica y Bioqumica, Ave. Tecnolo gico y Antonio Garca Cubas S/N, 38010 Celaya, Gto., Mexico Instituto Tecnolo

A R T I C L E I N F O

A B S T R A C T

Article history: Received 9 October 2008 Received in revised form 21 July 2009 Accepted 24 July 2009 Keywords: UAFB Bioreactor Azo dye Activated carbon Residence time distribution Dynamic model

An Upow Anaerobic Fixed Bed (UAFB) reactor packed with activated carbon was used to remove the azo dye Reactive red 272. The biomass grown on the activated carbon surface was composed of an adapted consortium of microorganisms. Residence time distribution test indicated that the reactor was a plug ow behavior. A dynamic mathematical model is presented for dye ux along the reactor and within the bioparticles composed of two regions: activated carbon core and biolm. The model considers that the reaction is performed in the biolm and in the liquid phase and includes dye transport by dispersion and diffusion. The concentration prole within the bioparticles changes with reactor height and time as the equilibrium is achieved. Changes in dye concentrations affect the concentration prole in the reactor and reduce the removal efciency. The effectiveness factor depends on the reactor height and on the dye concentration at the inlet. 2009 Elsevier Ltd. All rights reserved.

1. Introduction The degradation of azo dyes from textile efuents has been the objective of research for some years, due to the pollution problem they generate. Physicochemical, advanced oxidative and biological processes have been used in the removal of these compounds. However, an efcient and cheap process to eliminate this problem with low environmental impact is still unavailable. Perhaps the biggest problem is that reactive dyes are highly water soluble, due to the presence of sulfonated groups that are not reduced under the ordinary wastewater treatment processes [1 3]. Anaerobic bioreactors have an important role in the treatment of hazardous wastes, as they can degrade higher organic loads than aerobic reactors. Fixed bed reactors can be either immersed bed reactors, usually upow, or trickle bed reactors, which are usually downow. The main characteristic of xed bed reactors is that the biomass forms a biolm that covers a material that works as a support or carrier for the growth and maintenance of the microorganisms. Thus, the reactor efciency is improved, because the substratebiomass contact (effective surface area) is increased and the process is more stable. The carrier is used to improve the mechanical properties of the biomass and the cell retention, both of which contribute to the degradation process [4,5].

* Corresponding author. Tel.: +52 461 6117575; fax: +52 461 6117744. E-mail address: eleazar@iqcelaya.itc.mx (E.M. Escamilla-Silva). 1 Tel.: +52 442 2116034. 1359-5113/$ see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.procbio.2009.07.018

A biolm usually does not grow homogeneously on a support, but rather forms clusters on the supports surface. The internal structure of the biolm depends on the supercial velocity of the ow through the reactor, the mass transfer velocity and microorganism activity [6,7]. The degree of biomass formed affects the hydrodynamic behavior of the reactor. In the present work, an Upow Fixed Bed Bioreactor (UAFB) using activated carbon (AC) as a carrier was employed. It has been proven that AC possesses good properties for biolm growth and the removal of diverse pollutants [37]. In addition, AC might accelerate the degradation of azo dyes because of its redox mediator function, due to the chemical groups on its surface [8]. Di Iaconi et al. [9] proposed a mechanism for biolm growth: (1) formation of a thin lm covering the support by microorganisms, (2) increase of the biolm thickness, (3) breakage of the added biolm clusters and release of particles (biomass) due to the excess of growth, and (4) formation of a small pellet by detached particles. In this type of reactors, it is common to have bioparticles (carrier plus biolm), some free cells, and biomass pellets as a function of the supercial velocity in the reactor; the water owing through the bioreactor can reduce the drag by removing small biomass pellets. The mass transport through the bioparticles occurs during three phases: diffusion of the dye molecule from the solution to the biolm, diffusionreaction through the biolm, and adsorption diffusion through the carbon surface. One disadvantage of upow xed bed reactors is that the liquid ow is non-ideal, and thus, the dispersion, backmixing, and bypassing ows are considerable [10]. Therefore, it is important to

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that any discolor of the solution was not simply due to adsorption on to AC. The reactor was then inoculated by recirculating water containing 10% of an adapted sludge representative of textile wastewater environment. The aim is to complete azo dye reduction, especially reactive red 272, for a period of 15 days. Subsequently, 11.586 mg biomass/g AC was adsorbed to form a biolm on the AC surface. The reactor was operated using synthetic wastewaters containing the azo dye at different concentrations varying from 100 to 500 mg/L, as well as 1 g/L of dextrose and yeast extract as carbon and nitrogen sources for the microorganisms. 2.2. Residence time distribution A lithium chloride solution was used as a tracer in order to determine the hydraulic characteristics of the reactor and to obtain the residence time distribution. Smith et al. [11] used LiCl as a tracer and recommended a concentration of 5 mg Li+/L to avoid toxicity problems. We applied a 1-min pulse of a 2000 mg/L LiCl solution. Dextrose and yeast extract (1 g/L) were used as substrates during the test. Samples were taken from the reactor efuent every 30 min over 10 h (approximately 3 times the half-residence time (RTm)). The Li concentration was analyzed with an atomic adsorption spectrophotometer (PerkinElmer model 2280). The hydraulic residence time (HRT) should be better expressed as: R1 0 t C C 0 dt HRT R 1 0 C C 0 dt (1)

Fig. 1. Upow Anaerobic Fixed Bed (UAFB) reactor.

conduct the hydraulic characterization of the reactor using a tracer test. However, a plug ow is commonly considered to model the reactor. The modeling of such reactor allows the estimation of all its important functional parameters, the optimization of the efciency, the prediction of its behavior, and the future scaling. However, the scaling of a reactor from models made for laboratory reactors is difcult; there are factors, such as the transport between static and dynamic zones, which are negligible for small reactors, but must be included in real reactor models. Therefore, the main objective of this paper is to propose a mathematical dynamic model for an upow anaerobic bioreactor, UAFB, using AC as a carrier, that will result in improved biodegradation during the removal of the azo dye reactive red 272 (Lanasol Red CE). The mathematical model includes the following transport phenomena: convection, dispersion, diffusion and mass transfer from one phase to another along the reactor, and through the bioparticles, as well as dye reduction reaction. We have tried to ensure our model encompasses all the possible phenomena that occur in the reactor.
2. Materials and methods 2.1. Reactor assembling A 3.71 L UAFB anaerobic upow reactor made of Pyrex glass with a xed bed of 1.244 L (43.75% of its operation volume) was used. The reactor is depicted in Fig. 1 and its characteristics are shown in Table 1. At the beginning of the operation, an adsorption stage was performed to saturate the AC with the dye; thus ensuring

where C is the tracer concentration at a time t and C0 is the tracer concentration at t = 0. The parameters and non-dimensional numbers necessary to describe the reactor as well as the axial dispersion and mass transfer coefcients were calculated according to the following equations. clet number (Pe). These numbers indicate the Dispersion number (d) and Pe dispersion grade in the reactor. A Pe value above 1 indicates that convection is the leading factor in the mass transport; for Pe values below 1, dispersion is the leading factor. The numbers are given by [12]: Pe uL 1 D d (2)

1 s2 DC D 2 RT m uL

(3)

where u is the supercial velocity in the reactor, L is the longitude, and D the axial dispersion coefcient. Dispersion coefcient (D). It can be calculated by the dispersion number or by other correlations as the presented with the Reynolds number. D duL 1:01nRe0:875 (4)

Here, n is the kinematic viscosity of the water in the reactor [12]. Sherwood number (Sh) and mass transfer coefcient (km). Sh was calculated by the ssling correlation [13] that is applied to the mass transfer or ux around a Fro spherical particle. Thus, the following equation was used: Sh 2 0:6Re1=2 Sc1=3 (5)

The mass transfer coefcient of the dye was estimated by the following equation: km De f Sh dP (6)

where dp is the average particle diameter of the carbon particles and biomass in the bed. For this estimation, the dp value of the carbon particles at the beginning of the study (1.03 mm) was used; s 2 DC : variance, or a measure of the spread of the curve (Fig. 2) 2.3. Kinetic model The applied kinetic model to represent the dye biodegradation (reduction) was derived according to experimental observations. The proposed model expresses a change in reaction order and is given by Equation (7), where CA0 and CA are the initial and at any time azo dye concentrations, respectively, and k1 and k2 are the 1st and 2nd order specic reaction rates (h1, L/mg h). The deduction was explained in a previous paper [14]. rA dC A k1 C A k2 C A C A0 C A dt (7)

Table 1 UAFB reactor characteristics. Reactor volume, L Work volume, L Inside diameter, cm Inside diameter of the settle, cm Total longitude, cm Initial and steady state porosity of the bed Fixed bed volume, L Fixed bed longitude, cm Supercial velocity (average), cm/min Volumetric ow (average), mL/min RTm (average), min 3.72 3.3 6 9.5 105.5 0.53, 0.19 1.244 48 0.52 18 206.25

2.4. Dimensionless numbers model The dimensionless numbers that explain the transport process in the reactor were obtained from the dimensionless analysis of the model. These numbers are Biot number (Bi) that relates mass transfer to diffusivity, Fourier number (Fo) that relates the diffusivity in the reaction area to the reaction time, Wagner module (F2),

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Fig. 2. Experimental RTD with LiCl as pulse tracers applied to the reactor.

used to generate Thiele number (F), which indicates whether diffusion modies the reaction rate. From Thiele number, the effectiveness factor (h) is calculated, which relates the real reaction rate to the reaction rate without diffusion resistance. Thus, h expresses the inuence of the diffusion on the reaction rate. Thiele number is calculated by Eq. (8) (according to the proposed kinetic model there is a Thiele number for the rst-order term and other for the second-order term). The effectiveness factor for the discolor rate of the dye by volume unit of bioparticles was calculated using Eq. (9), according to the denition of volume average [14,15], and using the proposed kinetic model expressed in Eq. (7). Here, RA is the average reaction rate in the biolm and RA j is the reaction rate in the bioparticle surface in the liquid boundary; Fob is the characteristic Fourier number for the biolm dened in Eq. (19) in the next section. s k1 ; Deb R1
0 4 3

was closer to an ideal plug ow behavior. This effect can be attributed to the ne particles formed during the reaction time in the interparticle space in the reactor because these particles reduce the bed porosity and as a result the by-pass uxes. Kulkarni et al. [15,16] have shown that the ne particles formed in packed bed reactors reduce the by-pass ux because there is a better spreading of the ux and, therefore, a reduced dispersion. During residence time distribution tests biogas production occurs, due to the digestion of dextrose in the synthetic wastewater. However, the biogas production, with or without dye in the water, is not sufcient to consider the reactor as a mixed tank. Additionally, the rise of biogas through the bed is very slow and generates a by-pass ow due to the trapped biogas bubbles. When the supercial velocity in the reactor is increased, the bubbles are pushed and can ow better, and the by-pass ux is reduced. Thus, the reactor has a behavior that is closer to a plug ow [17,18]. The HRT was 1.61.8 times the RTm at low volumetric ows in the reactor and 1.11.3 times at high volumetric ows. The residence time distribution achieved for all the tests was tted by a statistical distribution of extreme value (FisherTippet), given by Eq. (10). It is a frequency distribution function for slant peaks. Pt y0 a expexp f 1 f 1 s 1 t tC f1 w (10)

F1 d

F2 d

s k2 C A0 Deb R 1h
0 2 2 F2 1 Fob vb F2 Fob vb vL vb j dj

(8) i

4p

RA j dj 3 pRA j

R1
0

R A j dj 3 RA j
2

2 F2 1 Fob vb F2 Fob vb vL vb j

RA RA j

(9)

3. Results and discussion 3.1. Residence time distribution The parameters and non-dimensional numbers that describe the transport in the xed bed reactor are given in Table 2. The supercial velocity was calculated as uL Q =eL pR2 i and the porosity of the bed eL was 0.19 at equilibrium. The hydraulic behavior of the reactor was approximated to a plug ow with axial dispersion; when Q was increased, the reactor

where P(t) is the normalized tracer concentration, y0 represents the distribution displacement (tracer concentration at time 0), a is the amplitude of the distribution, and w the width of the peak. These calculated parameters, the standard error and correlation coefcients are also given in Table 2. Fig. 2 shows the distribution of the residence time in the reactor for each test (P(t)) and the tted with described Extreme model equation (10). Iliuta et al. [10] have stated that a long tail in the residence time distribution can be caused by an axial dispersion in the dynamic ow and by a mass transfer between the dynamic and static zones. Also, when the packed bed of the reactor contains porous particles, as in the present case, the alteration in the residence time distribution can be attributed to an internal diffusion and a reversible adsorption of the tracer. Although this alteration is usually negligible, it does occur for the dye. The reactive red 272 dye molecule is reversibly and supercially adsorbed on this biomass and the AC surface, albeit only poorly; it has a limited adsorption capacity due to its molecular size and characteristics. There is an equilibrium between adsorption, reaction, and desorption. In our case, a constant saturation of the bioparticles is considered, and the adsorption dynamics are thus negligible.

Table 2 Hydrodynamic, mass transfer and tted extreme model Parameters for the UAFB reactor (L = xed bed). Parameter RTm (min) uL (cm/s) NReL BoL dL DL (cm2/s) PeL ShL kL (cm/s) y0 a w SEa R2b
a b

HRT1 57.264 0.0735 54.962 11029.2 2.864 10.026 0.349 45.403 0.0176 0.0270 0.5697 22.033 0.0255 0.9945

HRT2 66.203 0.0631 47.468 9461.54 2.255 6.828 0.443 42.246 0.0164 0.0470 0.6629 46.312 0.0443 0.9823

HRT3 66.203 0.0631 47.468 9461.54 2.407 7.287 0.415 42.246 0.0164 0.0251 0.6175 33.212 0.0325 0.9920

HRT4 42.412 0.0985 74.096 14769.2 2.332 11.022 0.429 52.283 0.0203 7.6 103 0.8944 29.893 0.0182 0.9977

HRT5 42.412 0.0985 74.096 14769.2 1.208 5.709 0.828 52.283 0.0203 9.3 103 0.6959 19.756 0.0226 0.9966

HRT6 42.412 0.0985 74.096 14769.2 0.413 1.953 2.420 52.283 0.0203 5.5 104 1.0029 32.259 0.0162 0.9980

Standard error of the t. Multiple correlation coefcient

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33

3.2. Dynamic model: transport and reaction in the xed bed After calculating HRT and all the necessary parameters and dimensionless numbers, a mathematical model was deduced and executed to represent the transport and reaction of the dye in the water upow through the reactor (the clarier zone is not considered here due to the complexity of the process). The dynamic model is based on the following assumptions: 1. The radial dispersion is negligible. 2. The reactor is divided into two zones: the xed bed and the clarier (not considered). There is mass transfer between them. 3. The dispersion coefcient is constant in each zone. 4. There is mass transfer between the water owing through the bed and the bioparticles. 5. The supercial velocity trough the bed is constant and calculated as uL Q =eL pR2 i. 6. The dye can be reversibly adsorbed on the bioparticles. 7. The dye is diffused, adsorbed, and reacts in the biolm. There is also supercial diffusion in the activated carbon core macro ) would limit the pores because the molecular size (21 A ). micropore diffusion (pore average diameter: 23.3 A 8. The particle is spherical and the biolm is uniform and porous. 9. The biomass on the activated carbon core grows to a certain thickness. Afterwards, the biomass excess detaches and forms small granules. Then, the biomass attached to the activated carbon goes back to its normal or equilibrium thickness. Thus, the biolm thickness is dynamic. However, considering that there is equilibrium between growth and detachment, an average thickness value is used. The model divides the bioparticle balance into two zones: zone I represents the AC particles (core) and zone II the microorganism biolm surrounding the AC core. The reaction term is included in two balance equations: in zone II of the bioparticles and in the liquid balance, because as it is an extracellular process there are free cells or small biomass granules in the owing liquid. Fig. 3 depicts a graphical scheme of the model with CAL the liquid

concentration of the dye, CAP the dye concentration in the AC core, and CAb the biolm concentration. The governing equations are: (a) Balance for the liquid ow in the xed bed.

@C AL @2 C AL @C DL uL AL K m asb C AL C Ab jrRB k1 C AL @t @Z @Z 2
k2 C AL C A0 C AL (11) This equation describes the dye convection, dispersion, and mass transfer from the liquid phase to the biolm surface and the reaction. The initial and boundary conditions are: t0 Z0 Z Lf C AL C A0 C AL C A0 (12)

@C AL 0 @Z

(b) Balance for the bioparticles. For the AC core:

2 @C A p 2 @C A p @ C A p De p r @r @t @r2

! (13)

This equation describes the dye convection and diffusion. The initial and boundary conditions that express eld equality at the interface are: t0 r0 r RC CA p 0

@C A p 0 @r
C A p C Ab

(14)

For the biolm (diffusion and reaction): ! 2 @C Ab 2 @C Ab @ C Ab k1 C AL k2 C AL C A0 C AL Deb r @r @t @r 2

(15)

Fig. 3. Transport and reaction model in the UAFB, Reactor scheme.

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lez-Gutie rrez et al. / Process Biochemistry 45 (2010) 3038 L.V. Gonza

This equation describes the dye convection, diffusion, and reaction. The initial and boundary conditions that express ux equality at the interface and mass transfer from the bioparticles to the liquid phase are: t0 r RC r RB CAb 0 @C A p @C De p Deb Ab @r @r @C Ab K m C Ab C AL Deb @r

Using the dimensionless numbers:

vp

CA p ; C A0

Fo p

De p L f ; R2 C uL 

t tuL t mL Lf

(22)

(16)

@vb @ vb 2 @vb Fob F2 Fob vb @t j b @j @j2

F Fob vb vL vb
2

For the biolm: " 2 

(23)

(c) Dimensionless model. The dimensionless governing equations are given next. For the liquid ow in the xed bed:

@vL @2 vL @vL 2 dL bm vL vb F1 Fob vL @t @z @z2

F2 Fob vL 1 vL t0
2

t 0 vb 0; @vb @v p j0 ab @j @j @vb j1 Bivb BivL @j

Using the dimensionless numbers:

(24)

(17)

vL 1 z 0 vL 1 @vL z1 0 @&

vb
(18) Bi

C Ab ; C A0

t t mL ;

tuL ; Lf Fob

F2 1
Deb L f

d2 k1
Deb

; : (25)

F2 2
K m RB ; Deb

d2 k2 C A0
Deb

d2 u L

Using the dimensionless numbers:

Deb ; De p

RC RC RB RC d

vL

C AL Z ; z ; Lf C A0 K a L bm m sb f uL

t tuL ; t mL Lf

dL

DL 1 ; PeL uL L f (19)

The reactor model, then, consists of three differential parabolic equations. To solve the model, all the parameters are previously calculated, and the spatial coordinates were discretized with nite differences, following time integration with a 5th order RungeKuttaFehlberg method. We coded this algorithm using FORTRAN 90. 3.3. Model solution We possessed the following data prior to solving of the model: from the AC properties: rp = 0.435 g/cm3 (density), ep = 0.1392 (porosity), RC = 0.0515 cm (average particle radius), and for the reactor: LL = 48 cm (longitude), Ri = 3 cm (radius), eL = 0.19 (bed porosity). The dispersion coefcient (DL), the dispersion number (dL), the clet number (Pe), the supercial velocity (uL), and the half Pe residence time (RTm), were estimated in the residence time distribution analysis, as previously explained in the methodology section. The diffusion coefcient was calculated by the method of Hines and Maddox [16], supposing a Knudsen diffusivity; the value of the coefcient was changed in order to t the model and to allow comparison with values reported in the literature for other dyes. The diffusivity in the biolm was assumed to be 100 times greater than the diffusivity in the AC core based on values reported for similar dyes [5,16,18]. The kinetic constants were estimated from experimental data and tted to model. The mass transfer surface of the bioparticles was calculated by Eq. (20) [19]. asb 6 6 db d p 2g (26)

F2 1

d k1
Deb

F2 2

d k2 C A0
Deb

Fob

Deb L f

d2 u L

To include the two zones of the bioparticles to become dimensionless, a parallel model was proposed. Thus, the AC core and the biolm are expressed as a single particle with a dimensionless radius varying from 0 to 1 (see Fig. 4): For the AC core: ! 2 @v p 2 @v p @ v p Fo p (20) 2

@t

j @j

@j

t 0 vp 1 @v p j0 0 @j j 1 v p vb

(21)

Fig. 4. Parallel, dimensionless model.

The parameters used to solve the mathematical model are given in Table 3. In our case, the Thiele number of second order is applied for an initial dye concentration of 250 mg/L. For 400 mg/L, it was 1.43 and for 500 mg/L, it was 1.60. This indicates that when the dye concentration is increased in the reactor inuent, the mass transfer effects are also increased, particularly the resistance to the diffusion. The dye removal is thus ceased.

lez-Gutie rrez et al. / Process Biochemistry 45 (2010) 3038 L.V. Gonza Table 3 Parameters used in model solution. DL (cm2/min) u (cm/min) Km (cm/min) Dep (cm2/min) Deb (cm2/min) k1 (min1) k2 (L/mg min) asb (cm2/cm3) Fop Fob
a,b c,d

35

423.4 3.786 0.984 2.58 105 2.58 103 3.046 1.47 102 36.81 0.091 36.404

Wa1a Wa1b

F F b a

c 1 d 2

Bi Bm dL

1.061 1.276 1.030 1.130 2 100 34.27 459.22 2.33

Wagner number. Thiele number (1.08 average). Fig. 5. Predicted concentration prole along the reactor. CA0 in mg/L.

Fig. 5 shows the concentration prole along the reactor at different dye concentrations of the reactor inow, and Fig. 6 shows the concentration prole within the bioparticles (AC core plus biolm) for an initial concentration of 250 mg/L. It can be seen in Fig. 6 that the particles close to the reactor inuent (z = 0.045) contain higher dye concentrations than the ones in the efuent zone, whose concentration is close to the dye efuent concentration. The concentration prole in the bioparticles changes with time as the bioparticles are saturated and reach equilibrium. However, a curved prole indicative of the reaction is observed in the biolm zone. Indeed, when the bioparticles are close to the efuent, the prole attens and the concentration is approximately uniform within the bioparticles. This is due to the lower dye concentration in that zone and therefore the reaction velocity is slower. The RTm in the reactor does not have much inuence on the removal of the dye according to the results predicted by the model. Fig. 7 shows the concentration prole along the reactor at different RTm conditions (see Table 4) and using an inow dye concentration of 250 mg/L. It is apparent that there is no noticeable effect on the concentration prole as RTm is incremented. However, the concentration prole in the bioparticles is altered in a different way by changes in RTm. Fig. 8 shows that as RTm is increased, the bioparticles are saturated faster. This is due to an increased contact time for adsorption and reaction and to an improved mass transfer between the liquid phase and the bioparticles. As a result, the RTm in the reactor affects only the mass transport rate in the reactor but not the biodegradation reaction. Thus, it

does not have an inuence on the concentration prole along the reactor and consequently on the removal efciency. Therefore, analyzing the proles depicted in Fig. 5, the main factor affecting the removal efciency is the inow dye concentration. Similar results were obtained by other authors. Spigno et al. [20] presented a mathematical model for the steady state degradation of phenol along a biolter reactor and obtained a concentration prole for phenol reduction at two different concentrations. They found the same prole for both concentrations, with a greater reduction in phenol at lower concentrations. Mammarella and Rubiolo [21] could predict the concentration prole for lactose hydrolysis in an immobilized enzyme packed bed reactor under different operating conditions. They obtained an asymptotic prole for lactose conversion along the reactor height and a much higher conversion at the lowest volumetric ow (100 mL/h). On the contrary, in our case the volumetric ow has much inuence. Those authors do not include the dynamic of the pollutant inside the bioparticles, as is shown in this work. o and Rodrigues [22,23] reported on the inuence of the Leita biolm thickness on the removal of a substrate when the support carrier material is, and is not, an adsorbent. They obtained the concentration prole within the bioparticles but in the absence of reaction. The proles showed saturation of the bioparticles with time, and the concentration increased as the biolm thickness

Fig. 6. Predicted concentration prole in the bioparticle at different t and z in the bed. Radius in cm.

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Fig. 7. Predicted concentration prole along the reactor at different RTm. Table 4 Parameters used in model solution at different RTm. RTm (min) Q (cm3/min) u (cm/min) Km (cm/min) dL 226.195 6.000 1.117 0.695 7.899 1099.8 0.308 123.4 24.21 81.429 16.67 3.102 0.913 2.843 519.7 0.111 44.42 31.78 75.398 18.00 3.351 0.939 2.633 495.1 0.103 41.13 32.70 67.859 20.00 3.723 0.978 2.370 464.4 0.093 37.02 34.07 54.287 25.00 4.654 1.083 1.896 411.5 0.074 29.62 37.75

Fig. 9. Predicted concentration prole along the reactor, increasing the reactor bed height (Lf). CA0 = 250 mg/L at the inlet.

efciency. A higher Lf implies more bioparticles and more time for the degradation reaction. However, most of the reduction of the dye is carried out in the lower third of the bed longitude. 3.4. Effectiveness factor The effectiveness factor (h) was calculated at different azo dye concentrations with the reactor inuent varying from 100 to 500 mg/L, and at RTm between 54.3 and 226.2 min. Each calculation was carried out using the predicted dimensionless concentration value in the biolm and in the liquid, and solving the model for a t = 2. The results indicate that the average reaction rate in the biolm and at the biolm surface is different at different reactor heights. Thus, the effectiveness factor is changed. Furthermore, the effectiveness factor depends mainly on the azo dye concentration [25,26]. Table 5 shows the results for different dye concentrations and Table 6 for different RTm. The change of the reaction rate as a function of the reactor height can be explained by the higher amount of active biomass at the inlet, i.e., at the bottom of the reactor. In this zone, dye and substrate concentrations (dextrose and yeast extract) are always higher and in consequence there is always a major reaction activity. Thus, most of the degradation of the dye takes place in this zone as shown in Fig. 6.
Table 5 Effectiveness factor values at different dye concentration. CA0, mg/L 100

bm
Fop Fob Bi

The rest of the parameters remain the same as in Table 4.

increased. However, it was not observed in the reaction zone in the o and Rodrigues [23] proposed an biolm as it was in our case. Leita intraparticle model for biolms on a carrier material including the convective ow inside the particle. They obtained the concentration prole and biolm thickness as a function of time. They concluded that bioreactors have to be operated under conditions that allow the liquid movement to occur in the void space of the biolm in order to improve mass transfer and, as a result, the efciency of the process. In biolms the hydrodynamics and kinetics of the system are related to the fact that most biolm reactions are diffusion limited. Therefore the shape of the concentration proles is determined by diffusivity and convection [23,24]. We hypothesize that the biolm is a continuous phase, even though it is not as biolms are formed by clusters, void spaces, and channels. Thus, the convection in the system is important and the measured diffusion coefcients are always approximations. This is shown in Fig. 8 as RTm in the reactor affects the mass transfer and, as a result, the concentration prole in the bioparticles. The effect of the bed height with a constant inlet dye concentration of 250 mg/L is shown in Fig. 9. It can be seen that the dimensionless dye concentration is reduced as the longitude of the bed height (Lf) is increased. This indicates higher removal

z
0.0455 0.1364 0.5000 1.0000

vL
0.8382 0.5962 0.1705 0.0593

vb jj1
0.8244 0.5862 0.1675 0.0578

RA jj1 31.6271 22.5320 6.4614 2.2318

RA 23.8782 17.2755 5.0965 1.7972 Average

h
0.7550 0.7667 0.7888 0.8053 0.7789 0.6944 0.7162 0.7585 0.7839 0.7382 0.6397 0.6639 0.7057 0.7310 0.6851 0.5534 0.5274 0.4225 0.3816 0.4712

250

0.0455 0.1364 0.5000 1.0000

0.8612 0.6593 0.3038 0.1977

0.8482 0.6490 0.2988 0.1922

32.2433 24.7535 11.4687 7.3753

22.3889 17.7281 8.6993 5.7812 Average

400

0.0455 0.1364 0.5000 1.0000

0.8828 0.7207 0.4708 0.4123

0.8705 0.7102 0.4635 0.4012

32.8209 26.8769 17.6518 15.1619

20.9943 17.8430 12.4575 11.0840 Average

500

0.0455 0.1364 0.5000 1.0000

0.8942 0.7529 0.5572 0.5211

0.8823 0.7424 0.5490 0.5077

33.1018 27.9572 20.7897 18.9753

18.3187 14.7441 8.7838 7.2410 Average

Fig. 8. Predicted concentration prole in the bioparticle at different RTm. Radius in cm. t = 2 and z = 0.045 (close to the inuent) in the bed.

lez-Gutie rrez et al. / Process Biochemistry 45 (2010) 3038 L.V. Gonza Table 6 Effectiveness factor values at different RTm. CA0 = 250 mg/L. TRm, min 226.195

37

z
0.0455 0.1364 0.5000 1.0000

vL
0.8572 0.6508 0.2936 0.1909

vb jj1
0.8390 0.6365 0.2868 0.1843

RA jj1 107.4324 81.8970 37.2383 23.9337

RA 74.7756 58.8457 28.3266 18.7967 Average

h
0.6960 0.7185 0.7607 0.7854 0.7402 0.6948 0.7168 0.7591 0.7843 0.7388 0.6946 0.7165 0.7589 0.7841 0.7385 0.6944 0.7162 0.7586 0.7839 0.7383 0.6939 0.7155 0.7578 0.7834 0.7376

the reactor and was function of the dye diffusion when the concentration was increased. The reported dynamic model could predict the dye and COD removal rate in a UAFB reactor by specifying its characteristics, dye inow concentration, and residence time. Acknowledgments This research was funded by Fondos Mixtos - Consejo Nacional a del Estado de Guanajuato (Project: 31756). de Ciencia y Tecnolog SAGARPA-CONACYT (200-C01-77). Appendix A. Nomenclature asb Bi C, CA C0, CA0 Cm d D De Fo HRT Km k1 k2 Lf Q rA RB RC Ri S t tm, RTm VP u specic surface of the particles, cm2/cm3 Biot number dye or tracer concentration, mg/L initial tracer, dye concentration, mg/L average concentration, mg/L dispersion number axial dispersion coefcient, cm2/s effective diffusivity coefcient, cm2/s characteristic Fourier number hydraulic residence time mass transfer coefcient, cm/s 1st order specic reaction rate, h1 2nd order specic reaction rate, L/mg h reactor bed height, cm volumetric ow reaction rate, mg/L h bioparticle radius, cm AC core radius, cm reactor internal radius, cm crosswise area to the ux, cm2 time half-residence time pore volume supercial velocity

81.429

0.0455 0.1364 0.5000 1.0000

0.8599 0.6566 0.3005 0.1954

0.8459 0.6455 0.2951 0.1897

39.1935 30.0168 13.8205 8.8786

27.2297 21.5163 10.4918 6.9636 Average

75.398

0.0455 0.1364 0.5000 1.0000

0.8606 0.6579 0.3021 0.1966

0.8469 0.6471 0.2969 0.1909

36.3521 27.8745 12.8735 8.2768

25.2495 19.9729 9.7693 6.4899 Average

67.859

0.0455 0.1364 0.5000 1.0000

0.8611 0.6591 0.3036 0.1975

0.8480 0.6487 0.2985 0.1920

32.7804 25.1616 11.6521 7.4926

22.7622 18.0212 8.8388 5.8734 Average

54.287

0.0455 0.1364 0.5000 1.0000

0.8625 0.6621 0.3071 0.2000

0.8506 0.6526 0.3025 0.1948

26.3450 20.2734 9.4520 6.0808

18.2815 14.5050 7.1630 4.7634 Average

The calculated effectiveness factor decreased from 0.78 to 0.47 when the dye concentration was increased from 100 to 500 mg/L, proving that when the dye concentration is increased the diffusion of the dye through the biolm has a major inuence on the reaction rate. This is reected by a reduction of the removal efciency. On the contrary, changes in RTm in the reactor at a constant inow dye concentration did not inuence the value of the effectiveness factor. Indeed, the effectiveness factor varied between 0.74 and 0.73 when RTm was decreased from 226.2 to 54.3 min. These values indicate that there is a slight effect of dye diffusion on the reaction rate when RTm is changed. 3.5. Conclusions The proposed mathematical model for a UAFB bioreactor was able to predict the concentration proles along the reactor and within the bioparticles (carbon core and biolm) for the biodegradation of a reactive red azo dye, using a kinetic model with a change in the reaction order. The proles at different inow dye concentrations showed an asymptotic curve with a major reaction activity in the lower zone of the reactor. The concentration decrease was reduced as the inow dye concentration was augmented. Nevertheless, the RTm has little inuence on the concentration prole along the reactor. In addition, the model predicts a larger removal rate as the longitude of the bed is increased for a same inlet dye concentration. The proles within the bioparticles illustrate the saturation of the particle and reect the zone of reaction in the biolm. Differences in the concentration values with respect to the reaction zone along the reactor could be observed. The saturation rate of the bioparticles changed with the RTm. With longer periods of time, the mass transfer was improved and the bioparticles were saturated faster without affecting the reaction. The calculation of the effectiveness factor showed that the reaction rate changed with respect to the position at the height of

Greek symbols

r e d z j v t
Wa

F bm a b
Subindex b L p 1 2

density, g/cm3 porosity biolm thickness dimensionless longitude dimensionless particle radius dimensionless concentration dimensionless time Wagner number Thiele number dimensionless parameter dimensionless parameter dimensionless parameter

biolm xed bed AC particle for the rst-order term for the second-order term

38

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