Nitrogen removal

The four basic processes are used : (1) ammonia

stripping, 2) selective ion exchange, (3) break point
chlorination, and (4) biological nitrification/denitrification.
Biological Denitrification. When a treatment plant
discharges into receiving stream with lowavailable nitrogen
concentration and with a flow much larger than the effluent,
the presence of nitrate (V) in the effluent generally does not
adversely affect stream quality.
However, if the nitrate (V) concentration in the stream is
significant, it may be desirable to control the nitrogen
content of the effluent, as highly nitrified effluents can
still accelerate algal blooms.
Even more critical is the case where treatment plant
effluent is discharged directly into relatively still bodies of
water such as lakes or reservoirs.
Biological nitrification/denitrificationis a two step
process.
The first step is nitrification, which is conversion of
ammonia to nitrate (V) through the action of nitrifying
bacteria.
The second step is nitrate (V) conversion (denitrification),
which is carried out by facultative heterotrophic bacteria
under anoxic conditions.
There are two groups of chemoautotrophic bacteria that
can be associated with the process of nitrification.
One group (Nitrosomonas) derives its energy through the
oxidation of ammonium to nitrite (III), whereas the other group
(Nitrobacter) obtains energy through the oxidation of nitrite
to nitrate(V). Both the groups, collectively called Nitrifiers,
obtain carbon required, from inorganic carbon forms.
Nitrification of ammonia to nitrate is a two step process:
Nitrosomonas Nitrobacter
NH
3
NH
4
NO
2
-
NO
3
-
This suggests that the rate-limiting step for the
conversion of ammonium to nitrate is the oxidation
of ammonium to nitrite (III) by the genus
Nitrosomonas.

c
= 1

where:
, the growth rate of Nitrosomonas at the worst
operating temperature.

c
sludge age (or mean cell residence time), in
a treatment plant must be sufficiently high if
nitrification is desired.
Microbiological Aspects of Denitrification
Nitrate (V) conversion takes place through both assimilatory
and dissimilatory cellular functions.
In assimilatory denitrification, nitrate(V) is reduced to
ammonia, which then serves as a nitrogen source for cell
synthesis.
Nitrogen is removed from the liquid stream by
incorporating it into cytoplasmic material.
In dissimilatory denitrification, nitrate (V) serves as the
electron acceptor in energy metabolism and is converted to
various gaseous end products but principally molecular
nitrogen,N
2
, which is then stripped from the liquid stream.
Because the microbial yield under anoxic conditions is
considerably lower than under aerobic conditions, a
relatively small fraction of the nitrogen is removed through
assimilation.
Dissimilatory denitrification is, therfore, the primary means
by which nitrogen removal is achieved.
A carbon source is also essential as electron donor for
denitrification to take place.
This source may be in the form of carbon internally
available in sewage or artificially added (eg. as methanol,
volatile fattyacids (VFA ).
Since most community wastewaters have a higher ratio of
BOD:N, the internally available carbon becomes attractive
and economical for denitrification.
Denitrificationreleases nitrogen which escapes as an inert
gas to the atmosphere while oxygen released stays
dissolved in the liquid and thus reduces the oxygen input
needed into the system.
Each molecule of nitrogen needs 4 molecules of oxygen
during nitrification but releases back 2.5 molecules in
denitrification.
Theoretically, 62.5% of the oxygen used is released
back in denitrification.
Only nitrification and denitrification are of interest when
calculating the oxygen consumption by nitrogenous matter.
Figure schematically shows the electron transfer in the
nitrification- and the denitrification processes.
Variation of the nitrogen oxidation number in the processes of
nitrificationand denitrification
In the nitrification process, the oxidation number of the
nitrogen atom in ammoniumincreases from -3 to +5 by the
transfer of 8 electrons to the electron acceptor (oxidant):
i.e. oxygen.
These electrons are accepted by two molecules (four
atoms) of oxygen (thereby changing its oxidation number
from 0 to -2).
For the nitrification of l mol of ammonium nitrogen
(14 g N), there is a demand for two moles (64 g) of oxygen,
so that the stoichiometric oxygen consumption can be
calculated as 64/14 or 4.57 mg O
2
mg N
-1
.
In the denitrification process, nitrate (oxidation number +5)
is reduced by organic matter to molecular nitrogen
(oxidation number 0), so that 5 electrons are transferred
per nitrogen atom.
The 8 electrons released by nitrogen in the
nitrification process, 5 electrons are recovered when
nitrate(V) is reduced to nitrogen.
In oxidimetric terms, the nitrate has an oxidation
capacity of 5/8 of the oxygen used in the production of the
nitrate by nitrification.
A fraction of 5/8 or 0.625 of the oxygen
consumption in the nitrificationprocess can be recovered
as equivalent oxygen in the process, i.e.
0.6254.57 = 2.86 mgO
2
mg N
-1
.
It can be concluded that there is a net oxygen consumption of
4.57 - 2.86 = 1.71mg O
2
mg N
-1
during complete biological removal of nitrogen.
Typical Flowsheets for Denitrification
Denitrification in suspended growth systems can be
achieved using anyone of the typical flowsheets shown in
the figure.
Separate stage sludge N removal
-3 to 5 day SRT
Figure: Separate stage growth denitrification process
MLE Process
Figure. Modified Ludzak-Ettinger process. A system with an anoxic
selector has the same process flow diagram, but with a smaller anoxic zone
Four Stage Bardenpho
Figure. Four stage Bardenpho process
More complete nitrification-denitrificationcan be achieved
by Bardenpho arrangement.
The first anoxic tank has the advantage of higher
denitrification rate while the nitrates(V) remaining in the
liquor passing out of the tank can be denitrified further in a
second anoxic tank through endogenous respiration.
The flow from anoxic tank is desirable to reaerate for
10-15 minutes to drive off nitrogen gas bubbles and add
oxygen prior to sedimentation.
The use of methanol or any other artificial carbon source
should be avoided as far as possible since it adds to the
cost of treatment and also some operating difficulties may
arise fromdosing rate of methanol.
Too much would introduce an unnecessary BOD in the
effluent while too little would leave some nitrates
undenitrified.
A more satisfactory arrangement would be to use the
carbon contained in the waste itself.
However, the anoxic tank has to be of sufficient detention
time for denitrification to occur which, has a slower rate;
since the corresponding oxygen uptake rate of the mixed
liquor is mainly due to endogenous respiration and is thus
low.
The denitrification rate, therefore, in a way also depends on
the F/M ratio in the prior aeration tank.
Consequently, if desired, a portion of the raw waste may be
bypassed to enter directly into the anoxic tank and thus
contribute to an increased respiration rate.
This reduces the sizes of both the anoxic and aeration tanks,
but the denitrification efficiency is reduced as the bypassed
unnitrified ammonia can not be denitrified.
By reversing the relative positions of anoxic and aerobic
tanks, the oxygen requirement of the waste in its anoxic
state is met by the release of oxygen from nitrates in the
recycled flow taken from the end of nitrification tank.
Primary settling of the raw waste may be omitted so as to
bring more carbon into the anoxic tank.
Conventional N removal involves coupling
aerobic nitrifires with anoxic denitrifiers
Conventional Nitrificatio/Denitrification
Table Relationship between expected biological nitrogen
efficiency and influent organic matter to nitrogen ratio
The single reactor system for nitrogen removal
is based on two core concepts:
1) that at temperatures between 30-40
0
C, the growth rate
of ammonia oxidizing bacteria is greater than the growth
of nitrite oxidizing bacteria;
2) denitrifying bacteria are capable of anoxic conversions
of nitrite to nitrogen gas. The reactor converts ammonia
mainly to nitrite by oxidation at a minimal sludge
retention time. The nitrite is then anoxically converted to
nitrogen gas.
Single reactor systems for High Ammonia Removal Over Nitrite
(SHARON)
SHARON is a very cost-effective treatment system for the
total removal of nitrogen components, through
nitrification/denitrification, from wastewater flow streams
containing high concentrations of nitrogen.
The system is used for the treatment of municipal
wastewater side streams from both dewatered digested
primary sludge and waste activated biosolids to achieve
high total overall nitrogen removal.
In addition it can be used to treat wastewater flows from
sludge dryers and incinerators.
SHARON is a high rate process operating with minimal
sludge retention time.
Due to differences in growth rates of the bacterial species
at the process design temperature (30-40C) a selection
can be made where in the nitrite oxidizing bacteria can be
washed out of the system while ammonia oxidizing bacteria
are retained along with denitrifying bacteria.
Using this metabolic mode of operation allows for a 25%
reduction in aeration energy required for nitrification and
a 40% reduction in the amount of BOD addition needed for
denitrification. In addition since the process is
accomplished in a side stream there are savings in
mainstream reactor costs.
The SHARON process is characterized by extreme process
stability, due to the high growth rate of bacteria and
the absence of sludge retention.
The sludge retention time is equal to the hydraulic retention
time, which means that the system basically controls itself.
The process will adjust even to strong variations in feed
conditions without operator intervention and will recover
from process disturbances in hours, rather than days.
Full treatment capacity can be maintained even when a
limited feed load is available, which allows for sudden
increases in load without adverse effects on effluent
quality. The system can be shut down for days without loss
of treatment capacity.
Bacterial activity increases at high temperatures.
At temperatures of 30-40
0
C nitrifying sludge needs a short
residence time. At those high temperatures nitrogen-rich
wastewater can treated in a single reactor.
No sludge retention is required to maintain the nitrifying
sludge in the system as long as the hydraulic retention time
is equal or highest than the minimum sludge retention
time.
SHARON is specially fit for treatment of nitrogen rich
wastewater, for example rejection water from the
dewatering of digested sludge at WWTP. Furthermore
Sharon is also fit for pr-treatment of various highly
concentrated industrial wastewater.
The SHARON process makes advantage of the difference
in growth rate of ammonia oxidizers and nitrite oxidizers
which is illustrated in Figure.
Figure Different growth rate of ammonia and nitrite oxidizers
Minimum aerated retention time
1 day
Nitrobacter
Nitrosomonas
Temperature
At higher temperatures, the ammonia oxidizers have a
significant higher growth rate.
By controlling the aerated retention time to approximately
1 day, the nitrite oxidizers will be washed out of the tank,
and nitrification will be limited to nitrite formation.
The SHARON process is operated in completely mixed
reactors without sludge retention.
Therefore the hydraulic retention time (HRT) is equal to the
sludge retention time (SRT).
Heating or cooling may be required to maintain a process
temperature between 30 and 40 C.
Usually an external COD source such as methanol is
needed because the BOD concentration of reject water is
low.
Caustic can be used for additional pH control.
In practice most SHARON plants operate without the use of
caustic and caustic is only used as back-up facility.
J et aerators or fine bubble diffusers are used for aeration.
The first SHARON plants were equipped with jet aerators.
Schematic
representation
of SHARON
influent
alkallnity
C-source
aeration
effluent
mixing
The nitrite route
As a result of N-removal by nitrite instead of nitrate energy and
COD are saved. Nitrification limited to nitrite saves 25% of
aeration energy.
Denitrification of nitrite saves 40% of COD, as is indicated in
Figure. More than 80% of the energy demand related to the
treatment of high strength ammonia wastewaters is contributed
to aeration energy.
Therefore a 25% reduction of the aeration energy is a
significant decrease of the overall energy consumption.
In addition 30% less surplus sludge is produced and overall
20% less CO
2
is emitted.
The advantage of a high conversion rate and the savings
on consumables demand makes the SHARON process a
compact and sustainable method for nitrogen removal.
The basic configuration of SHARON process consists of a
single, completely mixed tank.
The tank is aerated intermittently to accommodate
nitrification and denitrification.
An alternative configuration consists of two separate tanks,
one for nitrification and one for denitrification.
Water is recirculated between the two compartments.
An advantage of this configuration is a lower installed
aeration capacity because the aeration system can operate
continuously at design treatment capacity.
A disadvantage however is the need for a recirculation flow
which restricts the maximum denitrification efficiency and
requires an extra pump.
Depending on the site specific circumstances such as
space restrictions, wastewater characteristics, existing
available tank volume and minimum overall costs an
optimum system configuration is selected.
Nitrification
NH
4
+
+ 1.5O
2
NO
2
-
+H
2
O+ 2H
+
NH
4
+
+ 2O
2
NO
3
-
+H
2
O+ 2H
+
Denitrification
6NO
2
-
+3CH
3
OH + 3CO
2
3N
2
+ 6HCO
3
-
+3H
2
O
6NO
3
-
+5CH
3
OH + CO
2
3N
2
+ 6HCO
3
-
+7H
2
O
Results of rejection water treatment SHARON Rotterdam
parameter dimension value
TKN influent mg/l 1000-1500
N-removal % >95
HRT-oxic day 1-1,5
temperature
0
C 30-40
pH
-
6,8-7,2
oxygen
ppm
1,0-1,5

Discovered as late as 1986, it so far is the most unexplored
part of the nitrogen cycle. Given its basic features, the
anammox process is a viable option for biological
wastewater treatment.
The anaerobic ammonium oxidation (anammox), i.e. the
microbiological conversion of ammonium and nitrite to
dinitrogen gas, is a very recent addition to understanding
of the biological nitrogen cycle.
The first few years of anammox research have focused on
the basic properties of the process and on providing
evidence for its microbial nature and the principles of the
nitrogen and carbon metabolism.
It appeared that the anammox process is based on energy
conservation from anoxic ammonium oxidation with nitrite
as the electron acceptor and hydrazine as the intermediate.
CO
2
is used as the main carbon source for growth.
NH
4
+
+1.3NO
2
-
+0.13H
+
1.02N
2
+ 0.26NO
3
-
+ 2.03H
2
O
The necessary electrons are obtainedfrom the anaerobic
oxidation of nitrite to nitrate anammox physiology based on
mass balances over anammox enrichment cultures, the
anammox stoichiometry was estimated to be:
1 NH
4
+
+ 1.32 NO
2
-
+
0.066 HCO
3
-
+ 0.13 H
+
=
1.02 N
2
+ 0.26 NO
3
-
+ 0.066 CH
2
O
0.5
N
0.15
+ 2.03 H
2
O
Anammox is known to be active at temperatures between
6 and 43 degrees C. The pH range is 6.7 - 8.3 (optimum 8).
Under optimum conditions, the maximum specific ammonium
consumption rate is 55 micromol NH
4
+
/g protein/min.
The affinity for the substrates ammonium and nitrite is very
high (affinity constants below 10 mM).
Ammonia (100 mM) and nitrate (100 mM) do not inhibit the
anammox process.
The process is inhibited by nitrite concentrations higher than
20 mM.
When the nitrite concentration is more than 5 mM for
a longer period (12 h), anammox activity is completely lost.
ANAMMOX characteristics
Anaerobic
Autotrophic
Biomass yield: 0.05 kg VSS/kg N
Conversion rate: 1 kg N/kg VSSd
Min. doubling time: 11 days (biomass retention is important!)
Partial nitrification/Anammox is a new method for
nitrogen removal from wastewater.
It targets wastewater streams (or gases) high in ammonium
(>0.2 g/l) and low in organic carbon (C:N ratio lower than
0.15).
The two processes proceed as follows:
(partial nitrification)2NH
4
+
+ 1.5O
2
NH
4
+
+ NO
2
-
+ H
2
O +2H
+
(anammox)NH
4
+
+ NO
2
-
N
2
+ 2H
2
O
(total) 2NH
4
+
+ 1.5O
2
N
2
+ 3H
2
O + 2H
+
(the produced acid is balanced by the counter-ion of
ammonium, usually bicarbonate or sulfide)
Compared to conventional nitrification/denitrification, this
method saves 100% of the required synthetic carbon
source (i.e. methanol) and 50% of the required oxygen.
This leads to a reduction of operational costs of 90%, a
decrease in CO
2
emissions of more than 100% (the
process actually consumes CO
2
), and a decrease in
energy demand.
Wastewaters that are very suitable for treatment with
anammox are sludge reject waters ("sludge liquor") and
industrial wastewater (such as sour water) and gases.
The two processes can usually be engineered in two
separate reactors, or in a single vessel (the CANON-
concept, "Completely Autotrophic N-removal Over Nitrite").
The first full-scale anammox reactor was installed in
Rotterdam, the Netherlands.
Anammox is inhibited completely at oxygen concentrations
as low as 0.5% air saturation.
Under oxygen limitation (<0.5% air saturation), a culture
of aerobic and anaerobic ammonium oxidizers can be
obtained.
This culture converts ammonium directly to dinitrogen gas,
with nitrite as the intermediate.
Application of this concept in wastewater treatment can
lead to complete ammonia removal in a single, autotrophic
reactor.
This concept has been named CANON, meaning
"completely autotrophic nitrogen removal over nitrite (III)",
and referring to the way the two groups of microorganisms
interact: performing two sequential reactions
simultaneously.