~ Pergamon War. Sci.Tech. Vol. 39, No. I, pp. 23.5-243.1999.

4> 1999IAWQ
Published by Elsevier Science Ltd
Printed in GreatBritain. All rights reserved
0273-1223/99 $19'00 + 0'00
PIT: S0273-1223(98)00789-6

MODEL DEVELOPMENT FOR

SIMULTANEOUS NITRIFICAnON AND
DENITRIFICATION

Klangduen Pochana, Jiirg Kellerand Paul Lant

AdvancedWastewater Management Centre. Department ofChemical Engineering.
The University of Queensland. St. Lucia, Brisbane. Australia

ABSTRACf
The aim of this study is to simulate the behaviour of nitrogen and carbon compounds in a sequencing batch
reactor (SBR) by incorporating a dynamic microbial floc model. The results have shown that both floc
diameter and liquid phase concentration are important factors influencing the internal floc reaction rate. An
integrated model of the SBR has been proposed in this paper. whereby reaction rates are determined as a
function of internal floc concentrations. This enables the evaluation of the phenomena that occur due to
internal floc effects such as simultaneous nitrification and denitrification (SND). Results support the
hypothesis that SND is a physical phenomenon, and occurs due to oxygen diffusion limitations within floes,
@ 1999 IAWQ Published by Elsevier Science Ltd. All rights reserved

KEYWORDS

Diffusion limitation; dynamic modelling; floc modelling; SND; simultaneous nitrification and denitrification

NOMENCLATURE

a =radialdistancefrom the centerof a spherical floc, L

I?i =diffusivity of the component j in the floc, L-2T-l
dS/dt =rate of changeof componentj in floc, ML-3T- t
dSsjdt = rate of changeof component j in bulkliquid, ML-3T-I
dSjda =concentration gradientof componentj at any pointin the floc, ML-3L-l
rk =rate of k th reaction, ML-3T-l
R = radiusof the floc, L
Sf = feedconcentration. ML-3
So = effluentconcentration, ML-3 .
Vt =total liquid volume of the SBR including the volume occupied by the settle~ biomass and treated
supernatant remaining at the end of the decantperiodand the volume addedduringfill, L
=overallrate of reactionfor componentj, ML-3T- 1
= percentvolume of floc in each size range(i), dimensionless unit
=reaction rate of substrate j for a singlefloc size (i), ML-3T- t
= total volumeof the floc in mixedliquor. L-3
= numberof floc size
235
236 K. POCHANA et al.

INTRODUcnON

Sequencing batch reactor (SBR) technology is a cyclic activated sludge process that has been applied to the
field of BNR in both bench-scale experiments and full-scale installations. During the last decade, various
sequences of anaerobic, anoxic and aerobic conditions in the react period have been investigated to enhance
the biological activities in the SBR. As shown in previous studies (MUnch et al., 1994; Subramaniam et al.,
1994), the occurrence of simultaneous nitrification and denitrification (SND) in the aerobic period provides
a new alternative to increase the flexibility and possibly the overall performance of this process. The major
objective of achieving SND is to maintain similar nitrification rates as in fully aerobic systems but also get
significant nitrogen removal via denitrification at the same time.

Considerable research (Watanabe et al., 1992; Gupta et al., 1994; MUnch et al., 1994) has recently focused
on SND, although no dominant theory has emerged to date. The phenomenon has been extensively discussed
in both biological and physical aspects. The biological theory is that some heterotrophic bacteria can actually
denitrify in an aerobic environment (Robertson et al., 1988). In contrast, the physical theory is based on
oxygen diffusion limitations within the floc, creating a significant anoxic micro-zone inside the floes for
heterotrophic denitrification (Bakti and Dick, 1992).

One approach to achieve a better understanding of SND in terms of process behaviour and floccular
activities is to simulate the process based on a dynamic model of both the bulk liquid phase and microbial
floc phase. Previously, modelling has been performed using microbial floc models for different activated
sludge processes (Bakti and Dick, 1992; Tyagi et al., 1996). However, these were limited to steady state
simulations of single floes, Due to the specific operational conditions and process configuration, those
results are not directly applicable to the SBR process . The aim of this study is to dynamically simulate the
behaviour of nitrogen and carbon compounds in the floc. This behaviour will then be used at the macro level
in an SBR by incorporating actual floc size distributions.
Model for a sin le floc
A single floc model is used for
calculating substrate concentration
profiles insidethe floc.

The reactionrale for a sin Ie flocsize

A rate of reaction per unit volume
of floc is determined for each 3~
M JI -=-DJ
RI
da lleR,
individual flocsize.
Changing bulk liquid
concentrations affects
The overallrate of reaction for the
reactor is determined using the
contribution to the overall floc
~
OR, = v.. . L~MJI
.
The overallrate of reaction
substrate concentration
profilesinsidethefloc.
volume by flocs within different , '-I
sizeranges

The bulk liquid behaviour in the The reactormodcl

SBR is determined by modelling tiS" (St-So)Q
the SBR operation and dt = V, tOR,
incorporating thc effect of
diffusional limitation

Figure I. Overall flocand bulkliquidmodelling.

 Simultaneous nitrification anddenitrification 237

MODEL DEVELOPMENT AND MODIFICAnON

Oyerall model

This model aims to describe the behaviour of soluble nutrients in the bulk liquid phase by calculating
internal floc concentration profiles and reaction rates. Figure I illustrates the overall model consisting of
both liquid phase and floc phase. The model can be divided into 4 main steps which are (I) a micro level
model for a single floc, (2) the reaction rates for a single floc size, (3) the reaction rates for the entire reactor
considering the floc size distribution and (4) a macro model for the whole reactor including the operational
changes throughout the cycle. The details of each part of the model are described in the following sections.

Model for a Sjnl:le Floc

Several previous studies have simulated intra-floc concentrations for BNR systems . Bakti and Dick (1992),
Beccari et al. (1992) and Du et al. (1996) have all published pseudo steady state floc models concerning the
diffusion limitation of substrate into the centre of the floc.

To develop a single model, a number of assumptions are made. Some of these are major simplifications but
are necessary to achieve a workable model initially. They will have to be further tested in future stages.

the floc has a spherical shape

the transport of chemical species within the floc is by molecular diffusion
the floc density is taken as a constant
the mass transfer resistance through an interface between the liquid and the floc known as the
stagnant liquid layer is assumed to be negligible
the pH drop in the floc is assumed negligible
the reactions follow Monod kinetics
the diffusivity of a substrate is constant.

Oxygen
concentration

Figure2. Schematic oxygen concentration profilewithin a microbial floc.

The mass balance for a soluble compound within a floc may be written (see also Fig . 2):

(I)

The individual kinetic rates are based on a modified IAWQ Activated Sludge Model No. I (incorporating
nitrite as an intermediate in both nitrification and denitrification) (Henze et al., 1987).
238 K.POCHANA et al.

Reaction rate for a sin~le floc size

To accountfor the effectof diffusion limitation insidethe floc, the reactionrate insidethe floc is determined
numerically for each substrate. To simplify the model at this stage, it is assumed that the internal floc
concentrations reach steady state conditions at each time step. The reaction rate for a particularfloc is then
equal to the net mass flow of substrate through the surface of the floc. The overall rate of reaction can be
obtained by multiplying the flux at the outer surface by the external surface area of the floc. Equation 2
showsthe overallrate of reaction per unit volume of floc.

(2)

Overall reaction rate basedon floc size distribution

Undera specificoperating condition, the reaction rate depends on the size of the floc. Therefore, the reaction
rate corresponding to an individual sludge floc of a particular diameterdoes not represent the behaviour of
all floes in the system. The floes existingin an aerobic reactor are not all the same size but have a specific
floc size distribution whichinfluences the overall reaction pattern.

To determine the overall reaction rate of the activated sludge system, the contribution of floes within
different size ranges is taken into consideration. The overall rate of reaction in this system is therefore given
by equation (3).

(3)

SBRmodel

The development of mathematical models for SBR processes without incorporating internal mass transfer
resistance has typically been based on the IAWQ Activated Sludge Models No I or 2 (Henze et al., 1987,
I 99S). In this study, the overallreaction ratesare calculated basedon the approach described above.

The SBR cycle is continuously repeated beginning with the fill phase and ending with the draw phase. The
fill periodprovides for the addition of influent to the reactor. To simplify the model,it is assumed that there
is no biological reaction occurring duringthis shortfiU period. Therefore, the mass balancecan be written as
shown in equation(4)

~_ (Sf -S..)Q
dt - V, (4)

The react phase is dividedinto 2 stages: anoxicand aerobic. The non-aerated, mixed(anoxic) reaction phase
results in denitrification. The aerated reaction period provides for oxidation of the ammonia and carbon.
Equation (S) shows the overallreaction rate duringthe reactperiod.

(S)
 Simultaneous nitrification anddenitrification 239

Equation (5) applies to both the anoxic and aerobic period. In the anoxic period, no aerobic reactions occur,
due to the absence of dissolved oxygen (DO) in the liquid, whereas in the aerobic period, denitrification is
inhibited by the presence of DO.

RESULTS AND DISCUSSION

Experimental results

Based on the physical hypothesis, the effectiveness of SND should be dependent on the floc size and floc
size distribution. To investigate the effect of changing the floc size distribution on SND, a detailed analysis
of two subsequent cycles was performed. Both cycles were operated in the usual way but the activated
sludge floes were physically broken up between the two cycles. The first cycle was operated with the usual
floc size (median 80~m), whereas the second cycle was operated with smaller floes (median 40-50~m). To
reduce the floc size, the entire sludge from the reactor was subjected to high speed blending (24,000 rpm) for
5 minutes. Floc size measurements were performed during the first cycle, directly after blending and
throughout the second cycle to determine any reflocculation effects. The initial feed concentration of these
two cycles was 140 mg NH4-NIl, 1450 mg TCODIl, 204 mg SCODII. The dissolved oxygen during the
aerobic period was controlled in the range of 0.3-2.5 mg/l in both cycles. Additional experiments and model
simulations are underway to determine the impact of this wide range on the overall process behaviour.

Figure 3 shows the floc size distribution of the two subsequent cycles. Typical floc sizes in an SBR lab-scale
(Pochana and Keller, 1997), measured by a Malvem Mastersizer E, were 50-110 urn, which is relatively
large compared to 10-70 um as found by Andreadakis (1993). The floe size distribution showed a very
consistent pattem. It should be noted that the number of large floes was dramatically decreased by this
blending technique. During the 3 h aeration time, only a slight increase in floe size was observed due to
refloeculation.

12 - - Beforeblending
- Just afterblending
10 - - 1.5hrreflocculation
8 - - 3hr reflocculation

%6
vol
4

10 flocdiameter (ILm) 100 1000

Figure3. Flocsizedistributions priorto and following dissociation byhighspeedblending.

The concentrations of nitrogen compounds in the two cycles before and after blending are shown in Figure
4. In both cycles, the ammonium oxidation rate was identical, confirming that the blending procedure did not
affect the viability or performance of the biomass. Interestingly, no increase in nitrification rate was
observed due to the decreased floe size. This indicates that nitrification was not oxygen diffusion limited in
the initial cycle. In both cycles, the ammonia is completely oxidised. After the first 90 minutes of aeration,
no further reaction OCCUlTed. The remaining COD is likely non-biodegradable and therefore, together with
the relatively high DO level, limiting the denitrification proeess.

Comparing the oxidised nitrogen compounds, it Can be seen that the first cycle operating with a median floe
size of 80 ~m Can achieve 52% SND, whereas the SND activity decreased to only 21% after the floc size
was reduced. This result supports the hypothesis that a physical phenomenon is responsible for SND, in
particular the oxygen diffusion limitation whereby anoxic zones inside the floes are created. It has to be
240 K.POCHANA et al.

noted that a reduction of the median floe size from 80 JLm to 40 JLm represents a major reduction of the
available internal floc volume where denitrification could occur. Furthermore, the significant reduction in
the fraction of floes larger than 100 JLm further compounded this effect.
25

...... 20
~ 15
·1 10
§
~ 5

30 60 90 120 150 180 210

T~(min)

__ NH4-N(before) ___ N02·N(before) __ N03-N(beforc)

__ NH4-N(after) -e- N02·N(after) - 6 - N03-N(after)

Figure4. SND behaviourof the cycle beforeand after blending.

Mathematical modelJjn~ results

Different floc sizes are simulated in the model. The steady state profiles for floes with different diameters
are illustrated in Figure 5. The curves show that as the diameter of the floc increases, the oxygen
concentration near the floe center is substantially decreased. However, small diameter floes (up to about
6OJLm) show only limited decrease in the oxygen profiles and the internal concentrations remain relatively
close to the external concentration (lmgll in the case of Figure 5). Therefore, only large floes have the
potential to develop significant anoxic zones internally.
1 1--'=:::::;i===i===4~::::::"?Jt
~ 0.11 Diameter
a 0.8 (J.un)
! 0.7
-+-20
~ 0.8 _ _ 40
~ 0.5
~ 0.4 ......80
g 0.3 ~150
__ 300
.. 0.2
g 0+--.-+--_-
0.1
11"---+----1
0.2 0.4 0.8 0.8 1.0
diJPenslonless distance from center

Figure5. Oxygenconcentration profilel for floci with differentdiameters(externalDO of Imgll).

To study the effect of the high/low DO control range (DO on/off control with limits of 0.3 and 2.5 mgll), the
floc behaviour under these conditions at the beginning of the aerobic period was simulated. The floc was
divided into 5 micro-shells with dimensionless distances of 0.1,0.3125,0.525,0.7375, and 0.95 from the
center of the floc. Figure 6 shows the different pattern of the oxygen profiles inside the different floc sizes
(diameter 382, 155,77 and 33 urn). The DO level and the floc sizes used in this simulation corresponding to
the experimental studies described above. The results show that relatively large zones with permanently
anoxic conditions were created inside the larger floes. This enhances the denitrification activity inside the
 Simultaneous nitrification anddenitrification 241

floe significantly, whereas the temporarily low DO levels in the smaller floes are not likely contributing
substantially to denitrification.

0.7 -r------------, 2.0

0.6 Flocdiameter ISS j1IIl
~0.5 'i1.5
E 0.4 Sl.0
0 0.3
Q 0.2 8 0.5
0.1
0.0 .j...LCC:::::::::_--:..c~--~
o 2 4 6 2
time (min)
4 6
time (min)

2.5 -r-----------, 3.0

2.5
2.0
~2.0
~1.5 S1.5
8 1.0
0.5
8 1.0
0.5
0.0 .j..L_ _-+-..::::!l_-t--=----l 0.0
o 2 4 6 0 2 4 6
time (min) time (min)

Figure 6. Dynamic DO profiles at fivelevelsinsidefloeswithdifferent diameters.

It is also clearly shown that the bulk DO concentrations directly affect the concentration profile of substrate
inside the floes. These results are supported by Beccari et al. (1992) who reported that the reaction inside the
floes is not only related to the size of the floes but also corresponding to the bulk phase characteristics.

1. 0 . . . - - - - - - - - - - - - , 0.8 r-------~ __--,

~0.8 io.8
..S
SO.6
~ 0.4
~O.4
o io.2
ZO.2

2 4 6 2 4 6
time (minI tlme (min)

Figure7. Dynamic NOrN profiles inside floes withdiameter of ISS um (left) and77 J.lIIl (right).

0.20 0.20

~0.15 ~0.15
e
i o. l o
S
,; 0.10

§l 0.05 io.05

0.00 0.00
0 2 4 2 4 6
time (min)
6
° Ume (min)

Figure8. Dynamic N03-N profiles inside floeswith diameters of ISS j1IIl(len) and77 j1IIl (right).

Figures 7 and 8, respectively, show NOrN and N03-N concentration profiles inside floes of 77 and IS5 J1m
diameter. For the larger floe, the significant reduction of NOx-N in the inner sections of the floe clearly
indicates the denitrification activity present. However, floes with just half the floe diameter show very little
242 K.POCHANA et al.

difference between the internal and external sections of the floe and only display limited denitrification
activity. It is also remarkable how strongly the concentration profiles change between the two floe sizes. If
only the external part of the floe (O.95R) is compared, the profiles are still similar. However, they change
dramatically in the inner section of the floes, largely influenced by the significantly lower DO levels
achieved over most of the time inside the larger floes.

While only tQe start of the aeration period is shown in these figures. the ongoing trend remains the same for
most of the cycle (until the available carbon substrate becomes rate limiting). By comparing the nitrogen
produced in the different floes (results not shown), the actual net effect on SND from these floes can be
determined. Hoes of an average diameter of 382 um and 155 um achieved 98.5% and 26.3% SND,
respectively. whereas the smaller floes (diameter 77 um) only achieved 4.3% SND. Therefore. the
importance of the large floes for a high level of SND is clearly demonstrated and can likely explain the
significant reduction in SND activity shown in Figure 6. Further work is underway to directly simulate the
entire cycle with the actual floe size distribution as measured in the experiment to quantitatively validate
these findings. Based on these results. the oxygen diffusion limitation can be regarded as a reasonable
explanation of SND in such systems. The question of how to generate large floes, however, remains to be
investigated.

CONCLUSIONS

The dynamic floe model developed in this paper provides an insight into the micro and macro-scale
reactions occurring in suspended floc activated sludge systems. The model simulation is used to investigate
the effect of floc sizes and bulk liquid concentrations on the concentration profiles inside the floc particle.
Both floe diameter and liquid phase concentration are found to be important factors influencing the internal
floc concentrations.

The single floc model simulation has shown a result consistent with the hypothesis that denitrification can
occur inside floes due to oxygen diffusion limitation. The denitrification activity is thereby strongly
influenced by the floc size, but mainly for floes with a diameter above 60-80 um, The simulation results are
also supported by preliminary experimental findings whereby the floc size was found to have a significant
impact on the SND activity. Therefore, oxygen diffusion limitations are likely a possible cause for SND.

Nevertheless, the complex interactions in such systems may also depend on a number of other factors not yet
considered in this study. Therefore, an integrated model of the SBR is proposed in this paper and work is
continuing in this direction. This overall model of the SBR incorporating the dynamic microbial floc model
will then need to be experimentally validated.

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