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Effect of Recycle Ratio On N Removal
Effect of Recycle Ratio On N Removal
Effect of Recycle Ratio On N Removal
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Received 25 September 2002; received in revised form 17 June 2003; accepted 7 July 2003
Abstract
Internal recycle ratio is an important parameter in anaerobic/anoxic/oxic (A2 /O) wastewater treatment plant (WWTP) operation. An increase
in this ratio decreases nitrate and nitrite concentration in the effluent and hence improves the nitrogen removal efficiency, even though the
economical cost increases simultaneously. Determining the most favourable recycle ratio taking into account both considerations is an
important item in A2 /O WWTP operational optimisation. In this work, the effect of recycle ratio on nitrogen removal when using different
influent nitrogen loads was tested in a pilot A2 /O WWTP. Experimental results obtained show how increasing the internal recycle ratio from
0 to 5 produced a 12% increase in nitrogen removal. This increase was achieved by improving N–NOx removal by 9% with an increase in
N–NH4 + removal of 3%.
© 2003 Elsevier Ltd. All rights reserved.
0032-9592/$ – see front matter © 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0032-9592(03)00300-5
1616 J.A. Baeza et al. / Process Biochemistry 39 (2004) 1615–1624
Influent
ANAEROBIC ANOXIC OXIC SETTLER
(a)
(b)
Fig. 1. (a) A2 /O process for nutrient removal. (b) Implementation of the process in the pilot plant.
where denitrification takes place. The return sludge from the a WWTP and was formulated using compounds with differ-
settler is recycled to the anaerobic zone (external recycle), ent rates of biodegradability. The exact composition of the
where the influent and sludge are mixed under anaerobic wastewater is shown in Table 1. Ammonium chloride was
conditions. The alternate anaerobic/oxic conditions improve used at three different concentrations depending on the ex-
the efficiency of phosphorus removal by favouring growth periment. Wastewater characterization results are shown in
of phosphorus-accumulating microorganisms. Table 2.
Fig. 1b schematically depicts the nutrient removal process
in the pilot-scale facility, which consists of a 9 l anaerobic 2.3. Monitoring
selector (reactor 0), a 28 l anoxic reactor (reactor 1), two 28 l
oxic reactors (reactors 2 and 3) and a 60 l settler. In-line and off-line variables of the process were moni-
The hardware architecture [2,3] comprises a process tored in all experiments. In-line variables included flow-rates
computer (PC) and a programmable logic controller (PLC). (influent, internal recycle and external recycle), pH, redox
Every reactor of the treatment plant has in-line sensors (dis- potential, temperature, dissolved oxygen and actuation on
solved oxygen (DO), pH, ORP, temperature) connected to the aeration valves of the reactors. Off-line analyses for
probe controllers. All these controllers and the mechanical
elements of the pilot plant are connected to the PC and the
Table 1
PLC. The software for the PC, developed in C language,
Feed composition
includes graphic monitoring, data backup, PLC supervision
and control of key process parameters (DO, flow-rates, Component Concentration (mg/l)
stirring rates). This computer allows the WWTP to be con- Casein peptone 99
trolled via a set of predetermined setpoints. The DO control Ammonium chloride (NH4 Cl) 57/79/114
is based on a digital PID algorithm programmed in the Urea (CO(NH2 )2 ) 4.74
Starch ((C6 H10 O5 )n ) 103
computer, which modifies the airflow through the manipu-
Sucrose (C12 H22 O11 ) 78
lation of the pneumatic control valves of every reactor (via d(+)-Glucose (C6 H12 O6 ) 78
4–20 mA loop). Magnesium chloride (MgCl2 ·7H2 O) 78
Sodium chloride (NaCl) 69
2.2. Influent wastewater Potassium dihydrogenphosphate (KH2 PO4 ) 65
Calcium chloride (CaCl2 ·2H2 O) 34
Iron sulphate (FeSO4 ·7H2 O) 1.7
In order to obtain the required inflow (420 l per day of Zinc sulphate (ZnSO4 ·7H2 O) 1.7
wastewater of known composition), synthetic water was pre- Manganese sulphate (MnSO4 ·H2 O) 1.1
pared from two feed concentrates that were diluted with tap Yeast extract 0.86
water. The composition of the synthetic water was similar Copper sulphate (CuSO4 ·5H2 O) 0.86
Boric acid (H3 BO3 ) 0.086
to that typically obtained after primary settler treatment in
J.A. Baeza et al. / Process Biochemistry 39 (2004) 1615–1624 1617
Table 2 Table 4
Influent characterisation Experimental sets
Component Concentration (mg/l) Experiment FIR /FI (N–NH4 + )I (mg/l)
N–NH4 + 15.5/21.5/31.0 Set 1
N–Norg 10.8 I 5 15.5
N–NO3 − 1.4 II 2
COD 470 III 0
P–PO4 3− 15
Set 2
IV 5 21.5
V 2
VI 0
N–NH4 + , N–NO2 − and N–NO3 − , were determined by us-
Set 3
ing a continuous flow analyser (CFA) and a flow injec- VII 5 31.0
tion analyser (FIA) [2,4,5]. Total suspended solids (TSS), VIII 2
volatile suspended solids (VSS), Diluted Sludge Volume IX 0
Index (DSVI), COD, P–PO4 3− , N–Norg (organic nitrogen)
were determined using the protocols established in the ap-
plicable standard methods [6]. 2.5. Experimental design
3. Results and discussion imately an energy consumption five times higher. Part of this
energy is recovered due to the increase of nitrate nitrogen
For each experiment, TSS, VSS, COD, Ntotal , N–NH4 + , load to the anoxic reactor. Nitrate can be used as electron
N–NO3 − and N–NO2 − were measured at each sampling acceptor instead of oxygen (1 mg of N–NO3 − is equivalent
point (influent, reactors 0, 1, 2 and 3, external recycle and to 2.86 mg of oxygen) by the denitrifying microorganisms in
effluent), as well as the influent, internal recycle and ex- anoxic conditions. Hence, an increase in nitrate load to the
ternal recycle flow-rates. The collected data were used to anoxic reactor implies a higher COD removal in this reactor
evaluate nitrification rates and nitrogen removal efficiency. and, consequently, lower oxygen requirements in the aerobic
COD removal efficiencies in all experiments exceeded 95%, reactors. However, this energy recovery does not compen-
therefore these experimental results are not considered in sate the energy consumed for internal recycling. Thus, inter-
the discussion. nal recycle ratios as high as FIR /FI = 5 should be avoided
from an economical point of view, and only should be used
3.1. Nitrogen concentration in the effluent when necessary.
The nitrogen ammonium concentration in all the sampling
The importance of the internal recycle flow-rate for ni- points of the pilot plant for each experiment is represented
trate removal was observed by studying the behaviour of in Fig. 3. There was no dilution effect in the experiments
nitrate concentration in the effluent (Fig. 2). Nitrate concen- without internal recycle (III, VI and IX) since the concen-
tration was slightly lower than the concentration found in tration of ammonium in the influent, reactor 0 (anaerobic)
reactor 3 because of partial post-denitrification in the set- and reactor 1 (anoxic) remained constant when internal re-
tler due to the internal reserves of COD available for some cycle flow-rate was set to 0. Nitrification did not take place
microorganisms. As expected, Fig. 2 shows that the nitrate in these reactors, but hydrolysis of peptone occurred, pro-
concentration in the effluent decreases when the internal re- ducing ammonium from the organic nitrogen. Then a slight
cycle ratio increases. An increase of the recycle ratio from increase in the ammonium concentration was observed. In
0 to 2 had a greater effect than an increase from 2 to 5. In the remainder of the experiments, this tendency was not ob-
set 1, the increase in nitrate removal was very low possibly served because there was internal recycle, which implies a
due to the low ammonium load, which limited nitrification. dilution effect, and hence there was an homogenisation ef-
The results obtained indicate that by using a recycle ratio fect of the ammonium concentration among reactors 1–3.
of 2, good denitrification could be obtained. However, ele- The decrease of ammonium from reactor 1 to reactor 3 re-
vated ratios (for example, 5) are necessary in order to obtain flects ammonium removal due to nitrification, growth and
a very low nitrate concentration in the effluent. cellular maintenance. As explained below, a higher decrease
A high internal recycle is beneficial for nitrate removal, observed in the ammonium concentration in the experiments
but it can be economically non-profitable in case of an in- without recycle does not imply a higher nitrogen removal
fluent with low ammonium load. The economic cost of in- rate because of the different flows occurring at each recycle
ternal recycle is directly related to its flow. For example, an ratio. It is interesting to highlight settler behaviour in Fig. 3.
increase of internal recycle ratio from 1 to 5 implies approx- In all experiments a slight diminution of ammonium nitro-
Set 1
Set 2
4
Effluent N-NO3 (mg / litre)
Set 3
3
-
0
0 1 2 3 4 5
Internal recycle ratio, FIR / FI
35
Exp I
30
Set 1 Exp II
Exp III
Exp IV
25 Set 2 Exp V
N-NH4 (mg / litre)
Exp VI
Exp VII
20 Set 3 Exp VIII
Exp IX
+
15
10
0
Influent Reactor0 Reactor1 Reactor2 Reactor3 Ext. Rec. Effluent
Sampling point
Fig. 3. Ammonium nitrogen concentration in each sampling point in the different experiments.
gen concentration in the external recycle took place with ditions in which the reaction rate was near the maximum,
respect to the influent concentration to the settler (coming since it did not depend on the ammonium concentration
from reactor 3). In addition, a slight increase in the exit of (see Fig. 3). This type of behaviour appears for ammonium
the settler with respect to its influent was observed. These concentrations quite superior to 1 mg/l, the ammonium
variations took place because the settler did not work as a semi-saturation constant in a kinetic model of Monod type
pure separator, but biochemical and physical–chemical pro- according to bibliographical values [8].
cesses also occurred. In Fig. 5, the nitrification rate versus the internal recycle
ratio is represented for each one of the experimental sets. A
3.2. Nitrification rates higher nitrification rate around 0.05 g N–NH4 + /g VSS day
was observed in the case of internal recycle ratios of 2 and 5
Global nitrification rates based on ammonium consumed and ammonium influent concentrations of 21.5 and 31.0 mg
were calculated using the measurements performed. Eq. (1) N–NH4 + /l. This was the highest nitrification rate found in
was used for the calculation of the nitrification rate.
([N − NH4 + ]reactor 1 − [N − NH4 + ]reactor 3 ) · (FI + FIR + FER )
RN = 3 (1)
i=2 Vreactor i · VSSreactor i
where RN is the specific nitrification rate, expressed in g the pilot plant during the present study. In set 1, with an inlet
of N–NH4 + consumed/g VSS day. This calculation was concentration of 15.5 mg/l, the observed nitrification rate
made assuming that all the ammonium that disappeared was lower probably because aerobic reactors operated with
was consumed in nitrification. It should be noticed that ammonium concentrations below saturation levels. In the
the real values of nitrification rates were lower than this experiments of sets 2 and 3 without the dilution effect of the
value because ammonium nitrogen consumed for the cel- internal recycle (experiments VI and IX), lower nitrification
lular maintenance of the microorganisms was quantified as rates were also observed. Hence, internal recycle improved
nitrification capacity. observed ammonium removal rate.
The observed specific nitrification rates in every experi-
ment are represented in Figs. 4 and 5. 3.3. Total nitrogen removal
The nitrification rate versus the influent ammonium
concentration for different internal recycle ratios is repre- The main objective of these experiments was to evaluate
sented in Fig. 4. It can be observed that the nitrification the effect of internal recycle on the percentage of nitrogen
rate increased when influent ammonium concentration was removed. This value was calculated using Eq. (2).
increased in each internal recycle ratio compared. This in- Ninfluent − Neffluent
crease was higher when the influent concentration increased Nremoved (%) = × 100 (2)
Ninfluent
from 15.5 to 21.5 mg/l. The increase in concentration from
21.5 to 31.0 mg/l involved a lower nitrification rate increase, Ninfluent is the integrated sum of all the nitrogen forms in
indicating that the system was being operated under con- the influent (ammonium, organic nitrogen and nitrate) for
1620 J.A. Baeza et al. / Process Biochemistry 39 (2004) 1615–1624
0.07
Nitrification rate (g N-NH4 / g VSS d)
0.06
0.05
+
0.04
0.03
0.02
FIR / FI = 0
FIR / FI = 2
0.01
FIR / FI = 5
0.00
14 16 18 20 22 24 26 28 30 32
+
Influent N-NH4 (mg / litre)
Fig. 4. Specific nitrification rate in the oxic reactors vs. influent N–NH4 + .
a period of 1 day. Neffluent is the integrated sum of all the when the internal recycle ratio was increased from 0 to 2,
nitrogen forms in the effluent (ammonium, nitrate and nitrite) and 5.5% from 2 to 5. Hence, the total improvement was
for a period of 1 day. The contribution of organic nitrogen 12.3% when the recycle ratio was increased from 0 to 5.
in the effluent was not considered, because it was very low The main reason for these results is that the increase of the
compared to the other components. internal recycle ratio increases the nitrate load supplied to
Table 5 shows the contributions of the different nitrogen the denitrifying reactor, which is translated in an increased
forms to the plant influent and effluent over each 24 h period. total nitrogen removal.
The percentage of nitrogen as ammonium, nitrate and nitrite Individually, each set shows that removal percentages
in the effluent with respect the total nitrogen introduced in were lower when the influent load to the plant increased.
the influent is also calculated. These results indicate that the applied load in sets 2 and 3
The percentage of total nitrogen removed is represented were higher than the nitrogen removal capacity of the pilot
in Fig. 6a. Increase of the internal recycle for any ammo- plant. In these sets, nitrification rates were maximal because
nium concentration in the influent resulted in an increase of they were not limited by substrate and, although the mass
the percentage of total nitrogen removed. The average im- of nitrogen removed was slightly higher, the percentage was
provement obtained in the three experimental sets was 6.8% lower.
0.07
Nitrification rate (g N-NH4 / g VSS d)
0.06
0.05
+
0.04
0.03
0.02
Set 1
Set 2
0.01
Set 3
0.00
0 1 2 3 4 5
Fig. 5. Specific nitrification rate in the oxic reactors vs. internal recycle ratio.
J.A. Baeza et al. / Process Biochemistry 39 (2004) 1615–1624
Table 5
Characterization of the influent and the effluent, proportion of nitrogen removed and distribution of unremoved nitrogen species
Experiment N–NH4 + N–Norg N–NO3 − Ntotal N–NH4 + N–NO3 − N–NO2 − Ntotal N removed Removed N–NH4 + N–NO3 − N–NO2 −
influent influent influent influent effluent effluent effluent effluent (g per day) (%) effluent effluent effluent
(g per day) (g per day) (g per day) (g per day) (g per day) (g per day) (g per day) (g per day) (%) (%) (%)
I 6.510 4.520 0.600 11.630 0.970 0.286 0.000 1.256 10.374 89.2 8.3 2.5 0.0
II 6.510 4.520 0.600 11.630 1.084 0.357 0.118 1.558 10.072 86.6 9.3 3.1 1.0
III 6.510 4.520 0.600 11.630 1.310 1.138 0.256 2.705 8.925 76.7 11.3 9.8 2.2
IV 9.030 4.520 0.600 14.150 2.533 0.151 0.097 2.780 11.370 80.4 17.9 1.1 0.7
V 9.030 4.520 0.600 14.150 2.654 0.924 0.252 3.830 10.320 72.9 18.8 6.5 1.8
VI 9.030 4.520 0.600 14.150 2.743 1.592 0.307 4.641 9.509 67.2 19.4 11.2 2.2
VII 13.020 4.520 0.600 18.140 4.729 0.294 0.172 5.195 12.945 71.4 26.1 1.6 0.9
VIII 13.020 4.520 0.600 18.140 5.300 0.769 0.298 6.367 11.773 64.9 29.2 4.2 1.6
IX 13.020 4.520 0.600 18.140 5.489 1.420 0.336 7.245 10.895 60.1 30.3 7.8 1.9
1621
1622 J.A. Baeza et al. / Process Biochemistry 39 (2004) 1615–1624
95
Set 1 Set 2 Set 3
90
85
80
N removed (%)
75
70
65
60
55
0
I II III IV V VI VII VIII IX
(a) Experiment
45
Set 1 Set 2 Set 3
40
-
N-NO2
35
-
N-NO3
30
N effluent (%)
+
N-NH4
25
20
15
10
0
I II III IV V VI VII VIII IX
(b) Experiment
Fig. 6. (a) Proportion of nitrogen removed in each experiment. (b) Proportion of nitrogen remaining in the effluent and contribution of each nitrogen form.
Percentages of unremoved nitrogen forms (the last three Finally, the specific nitrogen removal versus influent
columns in Table 5) are represented in Fig. 6b to provide ammonium concentration and internal recycle ratio is repre-
complementary information to Fig. 6a. The different contri- sented in Fig. 7. These values were obtained using influent
bution of ammonium, nitrite and nitrate to the increase of and effluent compositions and considering VSS values. For
removal efficiency are noticeable. As expected, each set in- each experimental set (same influent composition) a con-
dicates that the decrease of nitrogen in the effluent is mainly tinuous increase in nitrogen removal was observed when
due to nitrate and nitrite decrease. Using data in Table 5, it increasing the recycle ratio, but it was not observed to be
can be calculated that an average increase in removal effi- an optimal value for this operational parameter. From a ni-
ciency of 12.3% occurred when recycle ratio was increased trogen removal point of view, the highest recycle rate may
from 0 to 5, due to a 9.4% average decrease of nitrogen be suggested, although economical considerations should
as nitrate and nitrite in the effluent and to a 2.9% average be taken into account to limit this value.
decrease of ammonium nitrogen in the effluent. The same These facts suggest the usage of different internal recycle
tendency in the three sets was observed when increasing ratios depending on the actual conditions in the WWTP.
the internal recycle ratio: nitrate and nitrite removal were Internal recycle improves the homogeneous distribution of
favoured but there was a slight improvement in ammonium microbial communities in the reactors, increases the effi-
removal at the same time. As previously detected in the ni- ciency of COD removal by denitrifying bacteria and can be
trification rate study, internal recycle increased the observed important for avoiding possible inhibition due to high am-
ammonium removal rate. monium concentration in the reactors. As tested in these ex-
J.A. Baeza et al. / Process Biochemistry 39 (2004) 1615–1624 1623
Fig. 7. Specific nitrogen removal rate vs. influent ammonium concentration and internal recycle ratio.
periments, a recycle ratio around 2 usually provides a proper of 1). Finally, when higher loads of nitrogen are detected a
compromise between removal efficiency and costs, there- higher ratio should be used in order to meet regulations.
fore this value can be recommended in most situations. The
highest recycle ratio should be recommended when a high
load of nitrogen is applied to the plant, and when usage of Acknowledgements
the previous conditions is not possible to meet regulations.
A control system can implement the above different op- This work was supported by the Spanish CICYT (projects
erational conditions in real-time when measurements of am- BIO94-0679-C02 and AMB97–0889–c03–01). The Depart-
monium, nitrate and nitrite are available on-line. An exam- ment of Chemical Engineering of UAB is the Biochemical
ple of application of such a control system can be found in Engineering Unit of the ‘Centre de Referència en Biotec-
previous reports [9,10]. nologia (CeRBa) de la Generalitat de Catalunya’. J.A. Baeza
received a pre-doctoral fellowship from the C.I.R.I.T. (Gen-
eralitat de Catalunya).
4. Conclusions
[6] Standard methods for the examination of water and wastewater. [8] Henze M, Gujer W, Mino T, Van Loosdrecht MCM. Activated Sludge
19th ed. Washington, DC: American Public Health Association, Models ASM1, ASM2, ASM2d and ASM3. London: IWA Scientific
American Water Works Association, Water Environment Federation; and Technical Report No. 1; 2000.
1995. [9] Baeza JA, Ferreira EC, Lafuente J. Knowledge-based supervision and
[7] Gabriel D. Design and automation of a monitoring system for nitrate, control of wastewater treatment plant: a real-time implementation.
nitrite and ammonium through flow analysis: application to a pilot Water Sci Technol 2000;41(12):129–37.
WWTP with nitrification and denitrification (in Catalan). Barcelona, [10] Baeza JA, Gabriel D, Lafuente J. Improving the nitrogen removal
Spain: MSc Thesis, Department of Chemical Engineering, Universitat efficiency of an A2 /O based WWTP by using an on-line knowledge
Autònoma de Barcelona; 1996. based expert system. Water Res 2002;36:2109–23.