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Abstract
The development and the preliminary evaluation of a mathematical model used to design a horizontal-¯ow anaerobic immo-
bilized biomass (HAIB) reactor applied to domestic sewage treatment is presented. The in¯uences of both the liquid super®cial
velocity and the bioparticle size on the overall reaction rate were examined. The size of the particle used as biomass support was
found to aect strongly the total volume of the designed unit since the eectiveness factor decreased as the bioparticle size increased.
On the contrary, the overall organic matter conversion rate was not substantially in¯uenced by the liquid velocity. Based on these
data obtained from the mathematical model, a pilot-scale HAIB reactor was constructed adopting some design parameters and
following the design criteria established. The HAIB reactor comprised a 14.5 cm internal diameter PVC tube with length of 14.4 m
divided in to ®ve stages of 2.88 m each. Polyurethane foam cubic matrices with 1 cm side were used as support for biomass im-
mobilization. The reactor was operated at a mean hydraulic retention time of 4.3 h at mean sewage temperature of 25 1°C and
mean liquid ¯ow rate of 20 L hÿ1 . A preliminary evaluation of the mathematical model proposed to design the HAIB reactor was
performed based on data of chemical oxygen demand (COD) pro®les along the reactor length. Although deviations were observed
between experimental and theoretical data, the proposed model was found to be suitable for predicting the overall behavior of the
reactor. Ó 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Wastewater treatment; Anaerobic process; Fixed-bed reactor; Domestic sewage; Mass-transfer; Kinetics; Mathematical model
0960-8524/00/$ ± see front matter Ó 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 0 - 8 5 2 4 ( 9 9 ) 0 0 0 7 7 - 2
236 M. Zaiat et al. / Bioresource Technology 71 (2000) 235±243
support or self-immobilized, permit the attainment of mass (HAIB) reactor, to be applied for treatment of pre-
high (hc ) even when low values of (hh ) are applied. For screened domestic sewage. Afterwards, the designed re-
most of the immobilized biomass reactor con®gurations, actor was constructed and assayed in order to evaluate
sludge recycle can be suppressed. Up-¯ow anaerobic the applicability of the model and the design criteria
sludge blanket (UASB) reactors, anaerobic ®lters and adopted.
expanded- or ¯uidized-bed anaerobic reactors are ex-
amples of immobilized-cell systems.
The design and scale-up of anaerobic immobilized 2. Mathematical model proposed to aid in design
biomass reactors has usually been carried out utilizing
empirical criteria. The utilization of such criteria makes A bench-scale HAIB reactor was ®rst built to treat
the system optimization very dicult, since the ``black- recycled paper wastewater (Foresti et al., 1995) and,
box'' approach has application strictly limited to the afterwards, it was applied for kinetic, mass-transfer and
boundaries within which the model was developed hydrodynamic studies (Zaiat et al., 1997a). The HAIB
(Wentzel and Ekama, 1997). The adoption of funda- bench-scale bioreactor used in all these previous exper-
mental criteria is essential for permitting the design of iments comprised a 1 m long glass tube of 0.05 m di-
heterogeneous units at desired organic matter degrada- ameter with total volume of 2 l. It was provided with a
tion rates. perforated tube of 0.9 cm diameter installed at its upper
Mass-transfer rates are very important in heteroge- part for gas separation and collection. Polyurethane
neous systems, since the materials may have to move foam was used as support for biomass immobilization in
from one phase to another. In such systems mass- all previous work and this material was chosen as sup-
transfer and the relative quantities of the various phases port in the pilot-scale unit.
can play an important role in determining the overall The studies performed in the bench-scale HAIB re-
reaction rate (Atkinson, 1974). Both mass-transfer and actor permitted the estimation of some fundamental
biochemical reaction rates must be evaluated for iden- parameters that were applied in the present work to
ti®cation of the slowest step. The quanti®cation of the develop a mathematical model for design purposes.
mass-transfer limitations becomes important for the Initially, the ¯ow pattern was considered to be
design of high-performance, immobilized cell systems. properly described by a plug-¯ow model. This assump-
This performance is directly related to the minimization tion was based on previous hydrodynamic studies car-
of such limitations, since the overall reaction rate in ried out by de Nardi et al. (1999) in the bench-scale
these systems can be reduced because of liquid and solid HAIB reactor. Afterwards, substrate consumption was
mass-transfer resistance. considered to follow a ®rst-order kinetic model in the
The liquid-phase (external) mass-transfer resistance speci®c case of domestic sewage. This assumption was
decreases as the liquid super®cial velocity is increased, based on kinetic data obtained for anaerobic degrada-
due to the decrease of the boundary liquid layer. Ac- tion of domestic sewage by Vieira (1996). The intrinsic
cording to Atkinson (1974), the in¯uence of the ¯uid characteristics of this wastewater and the low concen-
velocity on the overall rate of reaction is such that at trations of organic matter permitted the representation
high values the overall rate becomes essentially constant. of the biochemical reaction rate by a ®rst-order model.
However, this is true only if the external mass-transfer is In this case, the overall anaerobic degradation process
the limiting phenomenon of the overall process. In fact, can be reduced to only one step. This approach sim-
a global analysis, including external and internal mass- pli®es the model since only one kinetic parameter is
transfer besides the biochemical reactions, has to be necessary to describe the biochemical reaction rate. This
done to relate the sensitivity of the overall reaction rate parameter refers to the slowest step of the anaerobic
to the physical and biochemical process parameters. conversion. If several anaerobic degradation steps are
The solid-phase mass-transfer resistance is in¯uenced assumed, kinetic parameters of each step considered
by the size of the support particle, besides the charac- must be supplied to the model. In this case, the exper-
teristics of the inert support and biomass concentration. imental eort can be dicult and the results unsatis-
The diusion velocity increases as the particle size de- factory, since the experimental identi®cation of each
creases. Therefore, an operating parameter (ms ) and a step can be complicated. Moreover, the resultant model
design parameter (the size of the support for biomass can become complicated, making its practical applica-
immobilization) are intrinsically related and aect the tion dicult. However, the adoption of one-step an-
overall reaction rate and, consequently, the reactor aerobic degradation kinetic is an assumption to be
performance. proved and this was, perhaps, the major challenge of
A mathematical model, that includes mass-transfer this work.
and biochemical reaction rates, was proposed, and used According to these assumptions and assuming iso-
for designing a pilot-scale biological heterogeneous re- thermal condition, the substrate mass balance under
actor, the horizontal-¯ow anaerobic immobilized bio- steady state was as follows:
M. Zaiat et al. / Bioresource Technology 71 (2000) 235±243 237
( " #) Additionally, the knowledge of the pressure drop in
ÿ
L=DX k1 gD
ECOD 1 ÿ exp 100;
1 the bed
DP is important in order to choose suitable
e:ms liquid super®cial velocities and particle sizes. Such a
where ECOD is the chemical oxygen demand (COD) re- parameter was estimated by the Ergun friction factor
moval eciency; L, the length of the reactor; D, the according to Bennett and Myers (1974). The Ergun
diameter of the reactor; k1 , the ®rst-order intrinsic ki- factor (fD ) is de®ned as:
netic constant; X , the mean biomass concentration 150
within the reactor, based on its useful volume; g, is the fD 1:75:
6
Rem
overall eectiveness factor; e, the bed porosity and ms is
In this expression, Rem is the modi®ed Reynolds
the liquid super®cial velocity.
number, de®ned as:
The ®rst-order kinetic parameter (k1 or k1 X ) used in
the model is the intrinsic parameter estimated under ms qL dp
Rem :
7
conditions of mass-transfer resistance being negligible. lL
1 ÿ e
The utilization of intrinsic parameters provides a general The expression (6) is valid for Rem ranging from 1.0
model, which can be applied for any condition of mass- to 104 .
transfer limitation. The in¯uence of the mass-transfer The pressure drop in the bed was estimated by the
resistance on the overall reaction rate is considered in following expression:
the value of the eectiveness factor; that is a function of
fD Lm2s
1 ÿ eqL
the liquid-phase mass-transfer coecient, the eective DP :
8
diusivity of the substrate into the bioparticles and the dp e3
intrinsic kinetic parameter. In the expressions (7) and (8), dp is the bioparticle
The eectiveness factor can be expressed in terms of diameter; lL , the liquid viscosity; qL , the liquid density;
dimensionless variables for ®rst-order kinetics as: e, the bed porosity; ms , the liquid super®cial velocity and
L is the length of the designed reactor.
1 1 1 Bi A sequence of calculations based on the mathematical
g ÿ :
2
/ tgh
3/ 3/ 3/=tgh
3/ Bi ÿ 1 model was proposed to obtain the dimensions of the
In this expression, / is the Thiele modulus and Bi is reactor as length, diameter, useful and total volumes,
the Biot number de®ned as: besides the diameter of the tube for gas collection.
The mathematical model developed for designing
s
Vp k1 X HAIB reactors pre-supposes the provision of several
/ ;
3 parameters, which have to be chosen or determined
Ap De
previously. It is convenient to divide these parameters
k s Rp into operating, fundamental and physical.
Bi :
4
De The in¯uent substrate concentration, the liquid ¯ow
In the expressions (3) and (4), k1 is the ®rst-order rate (Q) and the bed porosity (e) are the operating pa-
kinetic parameter; ks is the liquid-phase mass-transfer rameters. The bed porosity must be evaluated from
coecient; X , the mean biomass concentration; De , the bench scale experiments. Polyurethane foam is com-
eective diusion of substrate into the particle; Rp , the pressible and the bed porosity will be in¯uenced by the
equivalent particle radius; Vp and Ap are the particle way that the support is compacted. Wet polyurethane
volume and super®cial area, respectively. foam must be used in bench-scale experiments in order
The liquid-phase mass-transfer coecient (ks ) is a to reproduce the condition of the foam inside the reac-
function of the physical properties of the liquid and the tor, since data of bed porosity provided by dry foam are
liquid super®cial velocity. Several relationships for esti- quite dierent from those obtained with the support
mation of ks are presented in the literature. A relation- containing water or biomass. The polyurethane foam
ship presented by Perry and Chilton (1985) was utilized softly compressed will provided a bed porosity of 0.4,
in this work as: approximately.
ÿ1=3 ÿ1 The mass-transfer and kinetic coecients are the
Ks dp lL ems qL dp fundamental parameters. The intrinsic kinetic parame-
DL qL DL lL ters must be estimated for each particular case (waste-
ÿ0:50 water/biomass) using methods presented in the literature
ms qL dp
1:90 :
5 (Shieh and Mulcahy, 1986; Kus and Wiesmann, 1995;
1 ÿ elL Vieira et al., 1996; Zaiat et al., 1997b). Such methods
In this expression, dp is the bioparticle diameter; DL , aim at the attainment of experimental conditions that
the substrate diusion in a liquid medium, lL , the liquid render the mass-transfer resistances negligible.
viscosity; qL , the liquid density; e, the bed porosity and The substrate eective diusivity in a particle (De )
ms is the liquid super®cial velocity. determines the mass transport inside the catalyst.
238 M. Zaiat et al. / Bioresource Technology 71 (2000) 235±243
Reliable design will not be obtained if this parameter Based on bench-scale experiments, a value between
is unknown. Idealistically, De would be estimated di- 0.1 and 0.2 was proposed for the ratio (DTS /D). Values
rectly from data obtained inside the pores of the ma- in this range allow good conditions for gas separation
trix. However, such experiments are expensive and and result in a relatively high useful volume with respect
slow. Alternatively, it can be estimated from experi- to the total volume.
ments in which the liquid-phase is monitored and De is The liquid super®cial velocity directly in¯uences the
obtained from a material balance. Willianson and liquid-phase mass-transfer rate. The value of the liq-
McCarty (1976) considered it adequate to regard the uid-phase mass-transfer rate increases with ms in a bed
eective diusivities (De ) of substrates in bio®lms as containing bioparticles. In a ®rst analyses it is desir-
being 80% of their value in water. This estimation has able to adopt values of ms as high as possible, to ob-
been well-accepted (Droste and Kennedy, 1987), tain maximum overall reaction rates. However, the
mainly due to the complexity of the experimental value of ms is limited by the value that determines the
procedures and mathematical analyses involved in the biomass washout from the support. According to
determination of De . However, the bio®lm composi- Zaiat et al. (1996), the application of ms higher than
tion and structure, besides the nature and character- 1.5 cm sÿ1 will result in washout of around 10% of
istics of the support material, may in¯uence the value volatile suspended solids from polyurethane foam
of De . In fact, Zaiat (1996) observed that the mean matrices.
value of the diusion coecient for glucose in poly- The size of the particle is directly related to the dif-
urethane foam bioparticles was similar to the value in fusion rate inside the particle and to the external mass-
water. Vela et al. (1999) reported a value for eective transfer. The intraparticle mass-transfer rate will be-
diusivity (De ) of 0:58 10ÿ5 cm2 /s for glucose in come higher as the particle size decreases; thus, it would
bioparticles of sodium alginate containing anaerobic be desirable to assume particles with size as small as
biomass. This De obtained corresponds to 77% of the possible in order to maximize the overall reaction rate.
value in water. Therefore, the results presented in the However, utilization of small particles can result in high
literature are very speci®c and they cannot be extended pressure drops in a ®xed-bed. Thus, the size of particles
to other systems. Simple and rapid methods must be that maximizes the overall rate while causing low bed-
developed in order to obtain data on De for a speci®c pressure-drops must be chosen.
system.
Diusion in a liquid medium (DL ) is described in the
literature for several compounds (Perry and Chilton, 3. Methods
1985). The DL value used in the model must be related to
the limiting substrate. 3.1. Design parameters and criteria
The physical parameters to be provided to the model
are the liquid density (qL ) and viscosity (lL ) that must be The fundamental and physical parameters were esti-
obtained experimentally for a given temperature. mated or adopted speci®cally for domestic sewage at
The criteria to be assumed and ®xed by the designer 25°C, the mean temperature of the sewage to be treated,
are the organic matter removal eciency (expressed as while the operating ones were imposed on the model or
COD in this case) and the ratio between the diameter of obtained after wastewater characterization. These pa-
the tube for gas collection and the reactor diameter rameters are presented in Table 1.
(DTS /D). The liquid super®cial velocity (ms ) and the The in¯uent substrate concentration (Sbo ) provided
equivalent particle radius can also be imposed by the to the model was obtained after characterization of the
designer. However, these parameters must be obtained sewage to be treated, and a constant ¯ow rate (Q) was
by optimization procedures. assumed in this work in order to achieve better evalua-
The designer must ®x the expected COD removal tion of the mathematical model.
eciency. The assumption of very high eciencies can The ®rst-order kinetic parameter (k1 ) was estimated
result in very big units and the design can become eco- using the technique proposed by Vieira et al. (1996),
nomically impracticable, but in order to adopt this pa- because the experimental apparatus is simple (incubator
rameter, the designer can use previous experience with shaker) and the method for estimation of the parameter
other types of reactor treating the same wastewater. In is very quick. The value of the mean biomass concen-
this way, the capacity of the designed unit can be com- tration (X ) can be derived from the kinetic experiments.
pared with other units. It can also be evaluated from speci®c experiments car-
The ECOD can be used as a design safety factor. A ried out to provide data about the maximum ability of
value higher than expected can be assumed in order to the support to retain biomass. It was observed experi-
guarantee that the reactor provides suitable results, even mentally that polyurethane foam matrices were able to
under adverse conditions such as organic overloading, retain 23 mg of volatile suspended solids m Lÿ1 of foam.
for example. However, this value is based on a small number of ex-
M. Zaiat et al. / Bioresource Technology 71 (2000) 235±243 239
Table 1
Parameters used for HAIB reactor design applied to domestic sewage treatment
Parameter Value Source
ÿ1
In¯uent COD 350 mg L Sewage characterization
Q 20 L hÿ1 Constant parameter, ®xed for design
Bed porosity (e) 0.4 Experimentally obtained (polyurethane foam softly compressed)
k1 7:51 10ÿ5 L mg VSSÿ1 hÿ1 a
Experimentally obtained
De 4:97 10ÿ3 cm2 hÿ1 Perry and Chilton (1985)
DL 4:97 10ÿ3 cm2 hÿ1 Perry and Chilton (1985)
lL 0.0089 P Experimentally obtained
qL 1.19 g mLÿ1 Experimentally obtained
a
VSS Volatile Suspended Solids.
perimental observations and a high degree of uncer- were allocated along the reactor length in order to ob-
tainty can be associated with it. tain pro®les of some monitoring parameters.
The eective diusivity (De ) was assumed to be the
diusion coecient in water (DL ) based on the results 3.3. Operation and analytical procedures
obtained by Zaiat (1996), due to the diculty of estab-
lishing a suitable experimental method. In addition to Pre-screened domestic sewage was pumped to the
this, the complexity of the sewage makes the identi®ca- reactor at a constant ¯ow-rate of 20 L hÿ1 as de®ned in
tion of the diusion rate-limiting substrate dicult. The the design phase. Samples along the reactor length (L/
data extracted from Perry and Chilton (1985) refers to a D 20, 40, 60 and 80) were taken after start-up of the
mean value of diusion of carbohydrates with molecular reactor in order to obtain data on COD to compare with
weights ranging from 1,000 to 100,000. the values predicted by the theoretical model used for
A Brook®eld viscosimeter and a simple densimeter design purpose. The analyses were performed according
were used to estimate the liquid viscosity (lL ) and den- to the Standard Methods for the Examination of Water
sity (qL ), respectively. and Wastewater (SMEWW, 1995).
The COD removal eciency assumed in this work In¯uent samples were taken during the day by auto-
(90%) was higher than that observed in other anaerobic matic sampler every two hours and kept for subsequent
reactors treating domestic sewage, as a safety factor for analysis in a ¯ask maintained at 5°C. The data obtained
the design. An intermediate value of 0.15 was assumed refer to composite samples taken over the day.
for the ratio between diameter of the tube for gas col-
lection (DTS ) and reactor diameter (D).
A speci®c liquid super®cial velocity (ms ) value as well
4. Results and discussion
as a speci®c equivalent sphere radius (Rp ) value were not
®xed for design purposes. Several values were initially
4.1. Application of the proposed model for designing an
tested in the model and the values that maximized the
HAIB reactor for sewage treatment
overall substrate uptake rate and minimized the pressure
drop in the bed were adopted.
Considering the design parameters adopted and the
imposed design criteria, a sequence of calculations was
3.2. Pilot-scale horizontal-¯ow anaerobic immobilized
biomass (HAIB) reactor Table 2
Characteristics of the HAIB reactor as designed based on rational
A pilot-scale HAIB reactor was constructed in order bases and the actual characteristics of the constructed reactor
to evaluate the proposed model and the assumed crite- Characteristic Designed Constructed
ria. The dimensions of the reactor obtained by the the- Diameter of the reactor, D (cm) 14.0 14.5
oretical model were slightly changed in order to make Length of the reactor, L (m) 13.7 14.4
construction using commercially-available PVC tubes. Diameter of the tube for gas separation, 2.1 2.0
The reactor was ®lled with 1 cm side cubic particles of DTS (cm)
Total volume, VT (L) 210.0 237.5
polyurethane foam (density of 23 Kg mÿ3 ), resulting in a
Useful volume, Vu (L) 190.0 217.2
bed porosity of 0.4 according to the design criteria Hydraulic retention time, (hh ) (h) 3.8 4.3
adopted. The characteristics of the designed and con- Liquid super®cial velocity, ms (cm sÿ1 ) 0.1 0.09
structed reactor are presented in Table 2. Expected COD removal eciency, 90 94
The reactor was composed of ®ve 2.88 m PVC tube ECOD (%)
Length to diameter ratio, L/D 98 99
stages in series (Fig. 1). Intermediate sampling ports
240 M. Zaiat et al. / Bioresource Technology 71 (2000) 235±243
Fig. 1. Sketch of the pilot-scale horizontal-¯ow anaerobic immobilized biomass (HAIB) reactor.
followed in order to obtain the dimensions of the reactor avoid cell wash-out from the polyurethane foam parti-
as length, diameter, total volume and diameter of the cles. A value of 0.1 cm sÿ1 was assumed in this work,
tube for gas collection besides the size of the particles since its application resulted in a reactor diameter cor-
used as biomass support. responding to that of a tube commercially available.
Initially, the eect of the liquid super®cial velocity (ms ) Afterwards, the in¯uence of the size of the particle on
applied to the bed on the total volume of the designed the total volume of the reactor and on the pressure drop
unit for various particle sizes was checked (Fig. 2). It in the bed subjected to the ms of 0.1 cm sÿ1 was evalu-
can be observed that, in this case, the volume of the unit ated. The size of the cubic particle was varied from a 0.3
(VT ) necessary to treat the wastewater with the eciency to 3.0 cm side, resulting in equivalent radii ranging from
imposed by the model is not in¯uenced by the liquid 0.19 to 1.86 cm. The results obtained from this analysis
super®cial velocity. A substantial decrease in the total are presented in Figs. 3 and 4.
volume was not observed as ms was increased, since the The size of the particle was found to strongly aect
eectiveness factor did not change substantially. How- the total volume of the designed unit as observed in
ever, the particle equivalent radius in¯uenced VT mainly Fig. 3. The eectiveness factor (g) increased as the size
due to the intraparticle mass-transfer. of the particle decreased (Fig. 5), resulting in higher
Any value of ms could be assumed for design purposes values of overall reaction rate and, consequently, in
since the liquid velocity did not in¯uence the total vol- lower values of the reactor volume necessary to attain
ume of the designed unit. However, a limiting value of the expected eciency. The eectiveness factor ranged
1.5 cm sÿ1 (Zaiat et al., 1996) must be used in order to from 0.63, for cubic bioparticles of 0.3 cm side, to 0.07
assumption of a high COD removal eciency as a cri- Shieh, W.K., Mulcahy, L.T., 1986. Experimental determination of
terion in the design stage. intrinsic kinetic coecients for biological wastewater treatment
systems. Water Science and Technology 18, 1±10.
The improvement of the model, without it becoming Standard Methods for the Examination of Water and Wastewater,
too complicated and impracticable for practical appli- 1995. 19th ed. American Public Health Association/American
cations, is a challenge to be confronted in future Water Works Association/Water Environment Federation, Wash-
researches. ington, DC, USA.
Vieira, L.G.T., 1996. Estimation of intrinsic kinetic parameters of
substrate utilization by anaerobic biomass (in Portuguese). M.Sc.
Dissertation, Escola de Engenharia de S~ ao Carlos (EESC)/Univ-
Acknowledgements ersidade de S~ao Paulo (USP), Brazil.
Vieira, L.G.T., Zaiat, M., Foresti, E., Hokka, C.O., 1996. Estimation
of intrinsic kinetic parameters in immobilized cell systems for
The authors acknowledge the ®nancial support re-
anaerobic wastewater treatment. Biotechnology Techniques 10,
ceived for this work from FINEP ± Financiadora de 635±638.
Projetos and the grant received from CNPq ± Cons- Vela, F.J., Gianotti, E.P., Zaiat, M., Foresti, E., 1999. Estimation of
elho Nacional de Desenvolvimento Cientõ®co e Tec- substrate eective diusivities of anaerobic bioparticles. Environ-
nol
ogico. mental Technology (in press).
Wentzel, M.C., Ekama, G.A., 1997. Principles in the modelling of
biological wastewater treatment plants. In: Cloete, T.E., Muyima,
N.Y.O. (Eds.), Microbial Community Analysis: The Key to the
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