6.

METHODS AND EQUIPMENT FOR

WASTEWATER ADVANCED TREATMENT

Advanced wastewater treatment involves additional processes intended to improve

effluent quality by removing suspended and dissolved substances left over from the
preceding conventional processes. Effluents from the secondary biological stage
still contain: a) suspended solids; b) non-biodegradable organic substances
resistant to bacterial metabolism; c) toxic or cancerous compounds; d) ions of
inorganic substances, such as calcium, potassium, nitrates, phosphates, sulfates,
chlorides, etc.; e) an indefinite number of synthetic organic compounds.
Advanced treatment consists in processes and technologies designed to
provide higher degrees of treatment, impossible to achieve by conventional
methods as utilized in the physical and biological stages.
The concern for advanced treatment became manifest after 1970, especially
for the removal of nitrogen and phosphorus compounds. Thus, the biological stage
can remove only 25 - 40% of the total nitrogen. These elements present particular
hazards to the environment as they accelerate the process of eutrophication in
water basins. The nutrients stimulate the growth of algae and the formation of
activated sludge. After 1980, attention has been focused on eliminating volatile
organic compounds, most of them being toxic to humans and living beings.
Today, advanced treatment is obligatory, being imposed by the necessity of
maintaining the ecological balance. The impact of treatment plants must also be
analyzed from the point of view of their effects on the environment. Important
amounts of carbon, nitrogen and phosphorus are still carried by plant effluents into
the receiving streams. Other polluting elements, the toxic ones, are also
discharged accidentally or deliberately in the natural wat.
Methods of advanced treatment are applied a) if the final effluent requires a
higher degree of treatment than the secondary process can provide, in order to
protect the environment and prevent eutrofication of natural waters; b) if the
effluent is intended for reuse, or c) if the receiving stream is utilized as a source of
water supply for townships.
In the selection of methods and technologies, the designer must take into
account: a) the self-purification capacity of the natural stream into which the
effluent is discharged; b) the costs of converting the water of the receiving stream
to potable water if captures are to be made downstream from the discharged point;

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Wastewater treatment. Technologies, installations and equipment

c) the costs of the constructions and installations for the proposed technology;
d) the costs of operation and quality control of the final effluent; e) the amount of
energy required for installations and equipment utilized for advanced treatment.
Classification of technologies for advanced treatment
These technologies can be classified by the type of the intended process, or
by their removal efficiency. Processes of advanced treatment can modify,
supplement or replace one or more phases of the conventional technologies. Their
purpose is either to reduce pollutant concentration prior to discharge, or to obtain
renovated water for reuse. In order to compare the various treatment processes,
we must take into account: a) the principal methods to be employed in pollutant
removal; b) the type of operations and processes involved in the technology; c) the
characteristics of the wastewater treated.
The selection of operations and technologies for advanced treatment, depends on: a) the capacity of the technology to meet the wastewater treatment conditions; b) wastewater type - its composition and concentration; c) the compatibility
of various processes and operations; d) the available means to carry out the
process; e) the characteristics of the environment and the conditions imposed by
them; f) the economic feasibility of the proposed system. Because of the special
conditions required for the removal of each refractory pollutant, the study on economic feasibility alone cannot be the determining factor in the design of installations for advanced treatment.
Table 6.1
Advanced treatment processes
Removed matter
Suspended solids
Ammonia
Nitrogen
Nitrates
Phosphorus

Recommended process or operation

Filtration; micro-screening
Biological nitrification
Nitrification /denitrification
Denitrification in separate stages
Washing in main stream elutriation

Nitrogen and phosphorus

Nitrification/denitrification
Phosphorus removal- biochemically
Air stripping; ionic exchange;
Breakpoint chlorination
Chemical precipitation with metal salts
Chemical precipitation with lime
Adsorption on carbon; chemical oxidation;
activated sludge
+ powdered activated carbon
Chemical precipitation;
ionic exchange; ultrafiltration;
reverse osmosis;
electrodialysis
Volatilization and stripping
with gas

Nitrogen
(physical process)
Phosphorus
(chemical process)
Refractory organic and
toxic compounds
Dissolved inorganic solids

Volatile organic
compounds

Type
PE. BEA
PE, BEA
PE, BEA
BEA, N
RW,
PE,RAS
RW, PE
BEA, BEA+
filtration
RW, BE,
BEA
BEA,
BEA+ fil tration
RW, BEA

RW, PE

PE Physical stage effluent; BEP biological stage effluent prior to secondary tank;
BEA biological stage effluent after secondary tank; RW raw water; RAS recirculated
activated sludge; N nitrification

Methods and equipment for wastewater advanced treatment

261

Fig. 6.1. Technological flow schemes for advanced treatment

A - biological treatment with activated sludge and filtration; B - activated sludge + filtration +
adsorption on active carbon; C - nitrification with activated sludge; D - nitrification / denitrification with activated sludge and using methanol as carbon pours; E - removal of phosphorus by activated sludge and metallic salt; F - nitrification / denitrification with activated sludge
and metal salt; G - removal of phosphorus in biological current; H - removal of nitrogen and
phosphorus by biological means and filtration; In - influent; Ef - effluent; PT- primary settling
tank; ST - secondary settling tank; AB - aeration basin with activated sludge; CB - contact
basin; AR - adsorption reactor with coal; Fl - filtration; N - nitrification; aR - aerobic reactor;
anR - anaerobic reactor; An - anoxic zone.

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Wastewater treatment. Technologies, installations and equipment

The principal processes are: a) conversion of ammonia nitrogen to nitrate by

an operation called biological nitrification; b) removal of nitrogen by nitrification denitrification; c) removal of nitrogen and phosphorus by biological methods; d) removal of nitrogen and phosphorus by physical and chemical methods: filtration,
coagulation + precipitation, adsorption, electrodialysis, reverse osmosis, distillation,
ionic exchange, extraction, freezing, air stripping of volatile pollutants.

6.1. Processes for the removal of nitrogen

compounds
Generally, municipal wastewaters contain nitrogen concentrations (BOD5 /N =4) in
excess of the value necessary for the biological process of carbon removal (BOD5 /
N = 20). Because of the young age of the activated sludge, biological processes of
moderate and high loadings are not accompanied by nitrification, and the excess
nitrogen remains in the effluent.
In wastewaters nitrogen is found in the form of ammonia and/or organic
nitrogen, either soluble or particulate. The soluble organic nitrogen is in the form of
urea, amino acids, proteins, amines. Raw wastewaters also contain mineral nitrogen, small quantities of ionic nitrates NO3 , nitrites NO 2 , ammonium NO+4 , ammonia NH3, nitrogen oxide NO. The physical stage eliminates the particulate material
and the biological process removes only a small part of the ammonium (about 30%
-adsorbed by the biomass). Therefore, the greater part of the nitrogen compounds
are left over in the secondary effluent in the form of ammonia.
An indicator of the nitrogen concentration in wastewaters is the total nitrogen,
determined by Kjeldahls method, TKN, which stands for the sum of organic and
ammonia nitrogen. Consumption of oxygen for the removal of nitrogen compounds
appears much later and, therefore, the nitrogen concentration is not included in the
BOD5 analysis.
Removal of nitrogen compounds is performed by: a) biological nitrification /
denitrification; b) ammonia stripping; c) ion exchange; d) breakpoint chlorination chlorination at a concentration value necessary for clearing the multiphase mixture
so that it forms an emulsified stratification.
Biological methods are the most efficient in nitrogen removal and their
efficiency rates can be improved by low-load oxidation processes characterized by
an organic loading in the basin of lb 0.5 kg BOD5 /m3 basin and day, and a sludge
organic load of ls 0.15 kg BOD5/kg DSS and day.

6.1.1. Nitrification
Nitrification is an autotrophic biological process in which nitrogen compounds are
converted to nitrates and nitrites by oxidation. Unlike the heterotrophic nitrification,
the autotrophic process uses inorganic carbon (carbon dioxide) in the synthesis of

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Methods and equipment for wastewater advanced treatment

new cells rather than organic carbon. As a rule, the number of nitrifying bacteria is
small, their rate of growth is still low and their increase depends on the
concentration of nitrogen and organic carbon.
Nitrification of ammonia nitrogen is a twostaged biochemical process carried out by various
groups of bacteria - nitrosomonas, nitromonas
and nitrosococcus. In the first stage, the ammonium NH4 is converted to nitrite, and in the second this is converted to nitrate through the effect
of a new group of bacteria - nitrobacter - when
part of the ionic ammonium is assimilated into the
cells. The two types of reaction furnish the energy
required for the cells to develop, and they can
take place in a single reactor.
Fig. 6.2. Aggregate oxygen deNitrifying organisms can be found in almost mand for carbon oxidation and
every aerobic process. Therefore, the oxygen de- nitrification - for raw untreated
mand for the aerobic processes covers for both water (a) and for treated water (b)
carbon oxidation and nitrification requirement. In
biochemical processes, oxygen is also useful in oxidizing the trivalent nitrogen at
its maximum valence NO3 .
The oxygen demand for the oxidation of ammonium to nitrate is 4.3 mgO2/mg
ammonium nitrogen - a value included in that recommended for design 4.57
mgO2/mg nitrogen.
The possibility of using biological processes with activated sludge for
nitrification can be estimated by the ratio BOD5 /TKN, where TKN is the index of
the total Kjeldahal nitrogen. The ratio values of BOD5 /TKN = 1 to 3 correspond to
staged systems of nitrification where the nitrification fraction of microorganisms is
estimated to be 0.2, but for ratio values of BOD5 /TKN >3 separate stages are
recommended.
Table 6.2
Relation between the fraction of nitrifying organisms and BOD5 /TKN ratio
CBO5/TKN
0.5
1
2
3
4

Fracie nitrificatoare
0.35
0.21
0.12
0.083
0.064

CBO5/TKN
5
6
7
8
9

Fracie nitrificatoare
0.054
0.043
0.037
0.033
0.029

The parameters influencing the nitrification process are: a) water pH, which
must be 7.0 - 8.0 - it can increase to 9.0 due to the rise in alkalinity; b) water
temperature - the reaction speed and the rate of bacterial growth decrease with
falling temperatures; c) inhibitors - toxic substances, for example; d) the age of the
activated sludge and aeration time; for moderate and high- load aeration, the
activated sludge is considered young because the process is just beginning,
whereas for low-load aeration, the sludge is already old and a process of advanced
nitrification may appear.

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Wastewater treatment. Technologies, installations and equipment

Generally, a process of nitrification at moderate temperatures is similar to the

conventional method with activated sludge, except for the fact that; a) oxygen
requirement is bigger and the quantity of oxygen supplied for nitrification must be
supplemented, and b) the quantity of residual dissolved oxygen must be
maintained at a level of minimum 1.5 mgO2/l.
Since the nitrification bacteria are strictly autotrophic with a slower rate of
growth than the heterotrophic ones, the detention time has to be longer than in the
ordinary oxygenation process. Also, the reduction in the pH due to bacterial
conversion needs to be corrected by addition of lime, soda or low-alkaline ashes to
the water.
The single-stage process of nitrification and carbon oxidation with activated
sludge. Nitrification may occurs in all treatment processes with activated sludge
irrespective of the variant adopted. Its outset depends on the detention time and
the quantity of oxygen fed to the reactor. Important for this process are the
following parameters: a) the concentration of ammonium and nitrites must be
maintained as constant as possible, with a deviation factor within a range of 2
between the maximum and minimum value; b) the ratio BOD5 /TNK; c) the
concentration of dissolved oxygen needs to be maintain above the minimum value
of 2 mg O2/l; d) the temperature can range between 3 - 30C; at a temperature
exceeding 12C the nitrification efficiency increases to over 85% with full
nitrification at over 20C; e) the optimum water pH is 7.6 - 8.4; f) the biomass
concentration must be within 1500 - 2000 mg DSS/l depending on the ammonia
load and temperature; g) the concentration of organic substances can be up to
60 mg BOD5 /l; higher values could disturb the process; h) the concentration of
toxic substances - heavy metals ions, amines, phenol, cyanides, sulfur-cyanides affects the process since the nitrifying bacteria are very sensitive to toxic agents.
The kinetics of the processes with activated sludge is valid in nitrification
processes as well excepting some slight operational changes in the parameters
described above. Also valid is Monods relation (4.1) for the specific growth rate
L
, where m is the maximum rate in idealized conditions and abundant
= m
Ls + L
substrate.
The rate of substrate utilization (mass/unit of time and volume) is expressed
mSL
kSL
by rN =
, or rN =
, where k = m/Y , and Y is coefficient of
Ls + L
Y (Ls + L )
maximum growth determined for a finite period of logarithmic growth (mass of
formed cells/mass of consumed substrate).
The rate of substrate utilization rN [timp-1] can be expressed by the relation
L L
kL
, where tr is the hydraulic detention time. This time is different
rN = 0
=
tr S
Ls + L
1
= YrN kd , where
from the design average detention time of the bacterial cell t rc
kd is the coefficient of endogenous respiration. For technical calculations, the
kinetic parameters have the following typical values: a) m = 0.7 [days-1] for
nitrosomonas and m = 1.0 [days-1] for nitrobachter; b) LS = 0.6[mg/l] for
nitrosomonas and LS = 1.4 [mg/l] for nitrobacter.

Methods and equipment for wastewater advanced treatment

265

The nitrification stage. If independent stages of nitrification and carbon oxidation are used: a) removal efficiency is best; a) the process is highly flexible and
feasible; c) the toxic substances will have a diminished effect on the process due to
the presence of biodegradable organics.

Fig. 6.3. Treatment plant with physical stage PS, biological stage (BA-aeration tank,
ST-secondary settling tank) BS, nitrification stage NS and chlorination basin CB

Selection of the operating parameters in the nitrification stage is dictated by

the removal efficiency of organic carbon. In processes with biological film, a
reduced concentration in organic carbon is preferable because it can eliminate the
clarification stage for the nitrification to follow. In the procedure with activated
sludge, the low level of carbon may lead to inconsistencies between the floc
formed in the secondary settling tank and the new floc arising in the reactor.
Hence, the need to balance the organic load and to maintain constant floc levels in
the nitrification system.
The method of nitrification in separate stages is calculated in the same way as
in the procedure with activated sludge. For small concentrations in ammonium, it is
recommended to have either full mixing or plug-flow type in the reactor. The
nitrification rate increases with the elevation of the temperature and the value of the
ratio BOD5 /TKN decreases. The nitrification rate will be determined experimentally
for each separate case in order to avoid difficulties in appreciating the nitrification
fraction in the multiphase mixture. The nitrification rate varies between 0.5 - 0.6
kg NH+4 N oxidat/kgs.s.v.zi / kg DSS per day depending on wastewater origin,
composition and temperature.

6.1.2. Biological nitrification and denitrification

Removal of nitrogen by nitrification/denitrification is the most efficient method; it is
characterized by high efficiency rates, great stability and feasibility; it requires small
space and moderate costs and permits relatively simple control. The method
consists of two basic stages: a) nitrification - the aerobic conversion of ammonium
to nitrate (NO3); b) denitrification - the anaerobic conversion of nitrate to gaseous
nitrogen. The method of nitrification - denitrification process is recommended when
a high rate of nitrogen removal is desired.
Denitrification is a biological process of converting nitrates to gaseous nitrogen under the action of biochemical catalysts- enzymes- in anaerobic conditions. It
occurs as an effect of straining aerobic bacteria which, from lack of oxygen, are
forced to take this element from nitrates and nitrites, thereby reducing the ions to
molecular nitrogen which is released into the atmosphere.

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Wastewater treatment. Technologies, installations and equipment

Denitrification occurs under the action of some specific autotrophic bacteria micrococcus denitrificans, thiobaccillus denitrificans and other common species of heterotrophic bacteria - pseudomonas, acromobachter, micrococcus,
and bacillus. The parameters favoring the denitrification process are: a) an optimum water pH of 6.5 - 7.5; b) a biomass concentration of 2000 - 3000 mg DSS/l
and a volatile part of denitrifying sludge of about 65%; c) temperatures of
10 - 20C; the concentration of organic substances should be closely watched
because off-limit values can result in non-stabilized effluents.
A balanced growth of the biomass is dependent on the values of the organic
substrate/total nitrogen ratio = BOD5 /TKN, which in urban sewage is 4 5, yet a
value of at least 20 is recommended. Therefore, the amount of nitrogen present in
wastewater is much higher than the required value for a normal growth of the
bacterial mass. This makes it necessary for the organic substrate to be produced at
the rate required by the biological process - a fact that can be achieved by
resorting to external sources of oxygen supply.
In order to make it possible it is necessary to have sufficient organic matter carbon source - for the conversion to gaseous nitrogen. The carbon source can be
either the organic matter present in the wastewater (internal source) or added
methanol (external source). This external source leads to a higher reaction rate
than that occurring in the endogenous respiration.
Since any source of excess carbon is found in the effluent in the form of
organic loading, it is necessary to have an exact calculation of the concentration.
For instance, in the case of methanol the stoechiometric relation is
CM = 2,47 N0 + 1,53 N1 + 0,87 C0 [mg/l], where No is the initial concentration of
nitrate-nitrogen [mg/l]; N1 - the initial concentration of nitrite-nitrogen; Co - the initial
concentration of dissolved oxygen, [mg/l].
The global rate of denitrification is expressed by rDN = rDS 1,09 (T 20 ) (1 C0 )
[days-1] is the specific massic rate expressed in kg NO3 - N/kg VSS per day (see
values in Table 4.3), and Co represents the concentration of dissolved oxygen
present in the wastewater.
The detention time is expressed by t rDN = L0 L .
rDN S

The specific denitrification rate is given by the ratio of nitrogen mass removed
per day to the biomass utilized in the process, with values ranging from 3 to 100
kgNO N
3

kgssu zi

3 N

kgssu
zi

for endogenous respiration, and 30 to 300 kgNO

for outside

sources of carbon.
Table 6.3.
Specific rate of denitrification
Carbon source
Metanol
Metanol
Ap uzat
Metabolism endogen

rDS [kgNO3-N/kgSSV]
0.210.32
0.120.20
0.030.11
0.0170.048

Temperatura 0C
25
20
1527
1220

Methods and equipment for wastewater advanced treatment

267

An energy index is represented by the removable efficiency; this is determined

by the ratio of total nitrogen removed to total energy consumed during the
nitrification-denitrification process, for the aeration, mixing and pumping of the
multiphase liquid, expressed in kg TKN/kWh
Method of denitrification in separate stages. Denitrification is in fact a
stage added to a biological process during which the sludge is generated
independently in separate successive stage - carbon oxidation, nitrification and
denitrification. The specific installations employed for denitrification are: the basin
with sludge recirculation and continuous agitation with submerged mixers, the
biological filter, the system with biological slime attached growth to revolving
adsorbents and the method with fluidized bed.
The specific kinetic values of the denitrification process are: a) the maximum
rate of specific bacterial growth mDN = 0.3 days-1; b) the constant
LsDN = 0,1 mg NO 3 N / l ; c) Y =0.8 mg DSS/ mg NO3-; d) the coefficient of
endogenous respiration Kd = 0.04 days-1.
Application of the method of biological denitrification involves mixing and
maintaining the sludge floc in suspension. Mixing is carried out by mechanical
equipment, especially a totally submerged one. Submerged mixers have the
advantage of achieving homogeneity with maximum effects in some important
zones, especially those near the bottom of the reactor. At the same time, bottom
agitators generate reduced turbulence and make the circulation uniform. They
produce a free primary jet which comes out in the form of a cone with a vertex
angle of 6 - 10 and which, by dispersion and motion, generates currents
throughout the basin. The effectiveness of mixing is dependent, among others, on
the index of sludge volume (SVI). Thus, for a SVI = 125 - 90 ml/g the multiphase
medium is easy to mix, and for a SVI = 90 - 30 ml/g the aqueous mass is difficult to
mix. In general, mixing requires a large amount of specific energy per unit volume.
Combined system of nitrification/denitrification in a single stage with activated
sludge. This process eliminates the need of an external source of carbon (reduced
costs) and presents the following advantages: a) reduced oxygen requirements for
nitrification and removal of the organics; b) eliminates additional organic carbon
required for denitrification; c) eliminates intermediary settling tanks for sludge
recirculation. Such a combined system has a removal efficiency rate of 60 - 80%,
sometimes up to 85 - 95%.

Fig. 6.4. Nitrification process with prior-denitrification

268

Wastewater treatment. Technologies, installations and equipment

Method of nitrification with pre-denitrification. As illustrated in Fig. 6.4, the

process has two stages. In the first stage, the wastewater enters an anaerobic
basin where it is denitrified by help of the organic carbon present in the
wastewater. From the second basin of nitrification, the water loaded with nitrates
and the activated sludge is returned to the anoxic zone where it is contacted with
the organic substrate of the wastewater. The scheme proves efficient in removing
nitrogen and has the advantage of using economically the internal sources of
carbon. It eliminates the intermediary settling tank and thereby reduces investment
costs.
Method of nitrification with post-denitrification (Fig. 6.5). This procedure
utilizes the nitrification flux in the oxidation basin and denitrification in the anoxic
basin. As already pointed out, the use of the internal organic carbon speeds up the
rate of removing nitrates and reduces the volume of the anaerobic basin. The
disadvantage is an increased energy consumption for pumping and the need of a
supplementary secondary tank, which incurs additional investment and operation
costs.

Fig. 6.5. Nitrification process with post-denitrification

In the design and operation of nitrification - denitrification systems with

independent basins, it is recommended that the physical, chemical and kinetic
parameters affecting the process should have the values specified in Table 6.4.
They are given for a temperature of 20 C. For other temperatures, a correction
must be made according to the formula KT = K 20T 20 , where is a coefficient of
temperature.
Table 6.4.
Values of kinetic parameters for nitrification - denitrification
Process
Nitrification
Denitrification

Flow
Plug
Plug

trc days
820
15

tr days
615
0.22

S grssvu/l
2...3.5
12

pH
78
6.57

1.08-1.10
1.14-1.16

The discontinued method of nitrification and denitrification (Fig. 6.6). The

discontinued process permits nitrification (aerobic oxidation of ammonia) and
denitrification to take place in the same basin but in separate stages. Actually,
aeration takes place alternatively in a system with two basins. The aeration stage
creates aerobic conditions in the basin, which stimulate the oxidation of organic
substances and ammonia compounds (nitrification): when the air is cut off, anoxic
conditions set in producing reactions of denitrification. The problem becomes

Methods and equipment for wastewater advanced treatment

269

particularly important in processing wastewaters with low BOD5 /TKN ratios. The
advantage consists in reduced investment costs. The disadvantages consist in the
early decomposition and oxidation of the substrate and the reduction of carbon
contents. Another drawback is the possibility of having equal volumes in the two
basins, which incur higher costs for construction and operation.

Fig. 6.6. Discontinued nitrification - denitrification process

In the BIO - DENITRO scheme, either basin can work in aerobic - anaerobic
conditions, with staged phases and a returned circuit between the basins. The
main drawback is the equal volume of the aerobic and anaerobic zones and,
therefore, increased costs.
The Bardenpho method (Fig. 6.7) is a four-stage process recommended for
wastewater with reduced BOD5 /TKN values for which a high degree of nitrogen
removal is desired. The wastewater enters the first basin A - denitrification zone where it contacts the multiphase liquid, which is returned from the end of stage B of
combined nitrification and carbon oxidation.

Fig. 6.7. The Bardenpho method in four stages

The carbon present in the wastewater is utilized for denitrification, and the
nitrates are recirculated. The denitrification process evolves rapidly due to the high
organic loading. The ammonia present in the wastewater passes through the
anoxic basin to be nitrified in the first oxidation basin. The nitrified mixture in the
first stage A + B passes to the anoxic zone C where an additional denitrification
occurs using endogenous carbon as organic source. The last basin D is relatively
small and is principally used for stripping the gaseous nitrogen released through
denitrification. A new stage can be added to remove phosphorus.

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Wastewater treatment. Technologies, installations and equipment

The oxidation ditch, or the method of simultaneous denitrification is used

for both nitrification an denitrification - depending on whether the zone is anoxic or
aerobic. These zones are formed naturally differing in their position to the
mechanical aerators. Thus, the concentration of dissolved oxygen increases in the
zone of the aerator and gradually decreases downstream of the aerator due to
biochemical consumption, forming the anoxic region. The carbon resources
necessary for nitrification are created by introducing the influent to the limit of the
anoxic zone. Therefore, the two stages of nitrification and denitrification appear
simultaneously in the same basin, in which the motion is plug flow type being
generated by horizontal aerators. The effluent is discharged into the secondary
tank situated at the end of the aerobic zone. Removal efficiency is lower than in the
previous method because the scheme provides for only one anoxic region for
denitrification.

Fig. 6.8. Oxidation ditch for nitrification - denitrification

with activated sludge

The design of the combined system must have in view the recirculation
coefficient R, the detention time tr and other kinetic parameters of the process. If
the denitrification of recirculated nitrates is considered to be completed in the
anoxic stage and, by neglecting the assimilated nitrogen, the ratio of recirculation is
R =

LNi 4 LNe 4
1 , where LNi4 and LNe4 are the quantities of ammonia-nitrogen in
LNe 3

the influent, respectively in the effluent, expressed in mg/l, and LNe3 represents the
concentration of nitrate - nitrogen in the effluent in mg/l.
As nitrification occurs only in the aerobic zone, the detention time of the floc in
the combined method is trn = tr/Va , where tr is the time necessary for nitrification in
the conventional system, and Va is the volume of the aerobic portion. The massic
concentration in the reactor is given by the formula
S =

t rc Y (L 0 L )
t r (1 + k d t r )

(6.1)

The total aerobic detention time tra [days] is specified by the relation
t ra =

t rnYh (L0 L )
Y [1 + k d (fvss t rn )]S

(6.2)

where Yh [mgssv/mgCBO5] is the coefficient of heterotrophic growth with

accepted value of 0.55; L0 - L is the quantity of BOD5 removed from the system, in
[mg BOD5/l]; kd [days-1] is the coefficient of endogenous speed; S[mgD.S.S/l]; fvss is
the decomposition fraction of dry volatile solids in the oxidation process.

Methods and equipment for wastewater advanced treatment

271

As the decomposition fraction varies with solids detention time and the rate of
decomposition in the endogenous reaction of the volatile solids, the fraction can be
expressed by
fvss =

*
fvss

[1 + (1 f ) k t ] ,
*
vss

(6.3)

d rn

*
where fvss
= 0.75 - 0.80 is the decomposition fraction of volatile solids in the
mixture over a generation of maximum productivity.
The detention time in the anoxic medium is expressed by trDN = (1 Va )tra ,
where V2 is the volume of aerobic fraction.
The time necessary for denitrification in the anoxic regim is
*
t rD
N =

N DN
,
rD N L 0

(6.4)

where NDN is concentration the nitrate that needs to be denitrified [mg/l], VDN the denitrification rate with values listed in table 6.3, in [days-1].
*
If the two times are equal, t rDN = t rDN
, the calculation is correct; if not, the
calculation is resumed by introducing another fraction of aerobic volume.
All the schemes presented above necessitate: a) recirculation of the water sludge mixture with nitrates and nitrites; b) continuous agitation of the multiphase
medium to prevent settling of the floc; to obtain this, the mechanical mixers must
be of the submerged type since they generate a favorable hydrodynamic spectrum
in the biological process; c) the recirculated flowrate shall be 2 - 5 times greater
than the calculated value used in the selection of the pumps.
Complex procedure including pre- denitrification, nitrification and post - denitrification makes use of several basins, in a cascade arrangement. The denitrification
basins are fitted with submerged mixer designed to homogenize the multiphase
liquid continuously and to ease emission of gases. The aerobic basins for nitrification are equipped with aeration equipment that must ensure oxygen transfer and
the homogeneity of the multiphase mixture.

6.1.3. Methods of nitrification - denitrification with biological

slim film attached growth
The attached biological slime film is formed in biofilters (trickling filters) and in
biological revolving contact materials. The technology presents some advantages
especially in the case of low and medium biological loadings.
Biological filters. The degree of biological loading of the biofilter affects the
nitrification process because, at high loads, the bacterial film is dominated by
heterotrophic bacteria. In order to obtain efficient nitrification, the organic load must
be maintained within the limits specified in Table 6.5. In the case of biofilters with
plastic beds, the organic load must be higher than in those with rock beds,
because the contact surface area is by about 80% larger in the former. Thus, the
nitrification efficiency for ammonium will be 60% higher in systems combined with

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Wastewater treatment. Technologies, installations and equipment

carbon oxidation, which must also be provided with intensified ventilation in order
to obtain a more effective transfer.
The biofilter can be utilized as a single denitrification floor if it is placed after a
treatment plant with activated sludge design to oxidize carbon products. Commonly, the method utilizes two biofilters - one for degrading the organics and the
other for nitrification.
Tower filters have their beds filled with plastic bodies of various shapes and
large specific surface area. The filters are 6.6 m high and are provided with forced
ventilation. In view of the large surface area of the biological film, these filters are
recommended for nitrification processes. Their nitrification efficiency decreases
with the increase in surface load and decreasing temperatures. The nitrification
rate is optimum for surface hydraulic loads lower than 0.3 m3 / m2 and minute.
The Kaldnes method is a variant of the process with biological film. It consists
of an installation with at least two basins of reinforced concrete and covered
surface. The first basin is anaerobic, fitted with a submerged axial mixer, and the
second is aerobic, provided with air diffusers, which maintain the concentration of
residual oxygen at values between 4 - 6 mg O2/l. At this concentration, the
nitrification rate doubles. The filter medium consists of film-support elements made
of polypropylene in the form of small sprockets. These elements occupy 50 - 60 %
of the reactor volume, have a specific density close to that of wastewater and
provide a large contact surface area (350 - 450 m2/m3). In this way, the submerged
agitators (1.8 m in diameter) manage to maintain the plastic elements in continuous
motion. The circulation between the two basins is done through a special screen
(with 5 - mm openings), which permits free passage to the water while retaining the
plastic packing. The method can be employed for oxidizing carbon compounds in
nitrification /denitrification processes. For post - denitrification systems, the detention time is reduced to 2 - 3 hours and the removal efficiency is over 70%. Compared with the conventional procedure with activated sludge, the Kaldnes method
presents the following advantages: a) higher volume efficiency; b) eliminates
sludge recirculation; c) flexibility in operation; d) reduced load of suspensions;
e) small energy consumption - 0.3 kWh/kg COD.
Contact reactors. For the nitrification of the ammonium component, it is
recommended that the soluble organic load should be reduced to less than 15 mg
BOD5/l. The contact surface area is determined on the basis of the oxygen requirement for the biochemical oxidation of organic matter and for the reduction of
ammonia nitrogen. The sum of the two surfaces will represent the specific load
required by the combined process to take place.
Table 6.5
Values of specific load in biofilter
Process

Nitrification efficiency

Rock biofilter

7585
8595
7585
8595

Tower biofilter -plastic medium

Specific load
kg BOD5 /m3 and day
0.1600.096
0.0980.048
0.2880.192
0.1920.096

Methods and equipment for wastewater advanced treatment

273

6.1.4. Denitrification process in fluidized bed

In this process the nitrified wastewater passes in an ascending stream through the
fluidized bed of a vertical reactor (Fig. 6.8). The flow velocity must be high enough
to fluidize the bed of fine sand-type particles. The porosity of the fluidized medium
can be regulated by modifying the fluid flowrate that maintains the bed in suspension. Fluidization increases the specific contact surface, which, in turn, determines
an increase of the biomass concentration in the reactor. The compact installation is
easy to operate and can remove 12 - 16 kg /m3 and day.

Fig. 6.9. Biological reactor for denitrification with fluidized bed

6.1 5. Physical and chemical processes for nitrogen removal

Ammonia stripping with air. The method is based on removing ammoniumnitrogen by the volatilization of gaseous nitrogen. In the process the pH is corrected to a value of 10.5 - 11.5 by addition of limestone. The same reactant is used for
the removal of phosphorus. Because of high costs, the procedure is recommended
only for special cases and seasonal applications when the wastewater pH is too
high.
Breakpoint chlorination involves the addition of chlorine to the wastewater in
order to oxidize the ammonia present in the solution and convert it to gaseous

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Wastewater treatment. Technologies, installations and equipment

nitrogen and other stable compounds according to the chemical reaction 2 NH3 +
3HOCl N2 + 3H2O + 3HCl. The chlorine/nitrogen ratio is 8/1 - 10/1 when the
wastewater pH is 6 - 7. The method can be applied individually or in combination
with other unitary procedures. In order to increase the efficiency of the process and
reduce the costs, the debits and concentrations must be leveled off.
Ion exchange is carried out in a special installation where the ammonium ion
is retained by an activated natural medium - zeolite, clinoptylolite or other synthetic
media. By regenerating the activated medium, the retained ion is eliminated and
the capacity of the medium to retain ions is restored. The regenerating reactant can
be Ca (OH)2 when the ammonium ion is converted into a molecule of ammonia.

6.2. Methods for the removal of phosphorus

Wastewaters also contain compounds of phosphorus - an essential nutrient for
plant and animal growth. Significant amounts of phosphorus are contained in fertilizers, detergents and foodstuffs. In general, wastewaters contains about 10 - 12 mg
phosphorus /l of phosphorus, which can be removed by chemical or biological
reactions. Thus, 10 - 30% of the phosphorus contained in the influent is removed in
the secondary biological stage.

6.2.1. Biological procedures for the removal of phosphorous

The biochemical methods are based on incorporating orthophosphate, polyphosphate and cellular phosphorus. Depending on the specific environmental conditions, the phosphorus/nitrogen ratio in wastewaters is 1/7 - 1/3 and 1/5 inside the
cell.
The biological method consists in exposing the bacteria to alternate aerobic
and anaerobic conditions. During the process, the bacteria are being strained and
consume a great quantity of phosphorus. The cells use phosphorus for their life
support, for the synthesis of new cellular material and for energy transport.

Fig. 6.10. Scheme of combined process for phosphorus removal in main

stream of wastewater.

Removal by the main stream. This technology involves a combined process

by which both carbon and phosphorus are removed. The process occurs in two
basins - aerobic and anaerobic - where carbon and phosphorus compounds are

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Methods and equipment for wastewater advanced treatment

oxidized and eliminated by the action of activated sludge; if nitrification is also

desired, longer detention times are practiced in the aerobic stage. In the anaerobic
stage, the phosphorus contained in the wastewater and in the cells is retained as
soluble phosphorus, after being processed in the aerobic stage. The removal
efficiency depends on the ratio BOD/P in the influent. If the BOD/P > 10/1, the
content of soluble phosphorus in the effluent must be corrected to sub-unitary
values. If the BOD/P < 10/1, metabolic salts must be added in order to reduce
phosphorus concentrations.
Compared with other processes, the technology is relatively simple (Fig. 6.10).
The same technology can be utilized for nitrification. The resulting sludge contains
3 - 5% phosphorus and can be used as fertilizer. The disadvantages consist in the
low rates of nitrogen and phosphorus removal, the uncertain treatment performances obtained in cold weather and the high BOD/P values demanded by the
technology.
Table 6.6.
Typical design data for processes of phosphorus removal
Parameter

Unit

Food /biomass

Kg BOD5 /kg
VSS/day
Days

Detention time biomass

VSS
Detention time anaerobic
Detention time - aerobic
Biomass concentration
Recirculated sludge
Internal recirculation

Combined
Process
0.20.7

Stripping

Sequential
Reactor
0.150.5

0.10.5

225

1030

Hours

0.51.5

812

1.83.0

Hours
G/l
% influent
% influent

13
24
2540

410
0.65.0
2050
1020

14
23

Removal of phosphorus by stripping. In this process, part of the activated

sludge is fed to a an anaerobic basin in which the phosphorus is stripped for a 8 12 hours detention time (Fig. 6.11). The phosphorus is removed along with the
supernatant and the depleted sludge is returned to the aeration basin. The supernatant is then treated with lime or other coagulants in an independent basin and
the resulting precipitate is separated in a tertiary basin. In this way, the phosphorus
in the effluent is reduced to less than 1.5 ppm, prior to filtration. The technology is
flexible and removal is independent of the ratio BOD/P. Drawbacks: the process
requires chemical reactants of coagulation - flocculation and the elimination of the
lime from the installation are problems for the operator. The method also requires a
higher concentration of dissolved oxygen.
Discontinued procedure with sequential reactor. The method employs
several basins with dephased cycle. From feed to discharge, each of the basins is
set to run in several phases. The succession of phases is so established as to
permit the oxidation of carbon products, nitrification, denitrification and the elimination of nitrogen and phosphorus. The procedure is flexible and easy to operate,
being recommended for small debits.

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Wastewater treatment. Technologies, installations and equipment

Fig. 6.11. Method of phosphorus removal by elutriation

6.2.2. Phosphorus removal by metal salts and polymers

For the removal of organic phosphorus, polyphosphates and orthophosphates, aluminum and iron salts are used. These chemical reactions can also remove part of
the nitrogen. The reactants may be added to either the primary or the secondary
settling tank.
In the primary reactor the aluminum salt (alum) or the iron salt (ferric chlorine)
reacts with the soluble orthophosphate to form a precipitate which is then removed
with the primary sludge. The doze is 1 - 3 metal ions to one ion of phosphorus.
Utilization of polymers as reactants requires a pH value of 5 - 7 and settling by
air bubbling.
Addition of lime requires a lime doze of 65 - 80% of the phosphorus content.
The hydroxide reacts with the soluble orthophosphate forming an insoluble precipitate. The lime raises the pH value to 11. After precipitation the effluent must be
recarbonated prior to entering the biological stage. The lime doze is 75-250 mg/l of
the Ca (OH)2 for a pH = 8.5 - 9.5.
In the second settling tank, the reactant may be added directly to the aeration
basin, to the secondary tank or to the water feed channel of the settling tank.
Addition of reactants to the secondary tank is also valid for installations with
biofilter. The aluminum or iron salt causes the metallic hydroxides or phosphates to
precipitate. The reactants can also enter into reactions with colloidal particles
forming precipitates that settle by gravitation.
The polymers are fed to the zones with intense agitation or to tanks with
internal recirculation. Mixing can be performed by static or mechanical equipment.
The mixing time is 10 - 30 seconds if done effectively.

Methods and equipment for wastewater advanced treatment

277

6.3. Special procedures of treatment

These procedures are designed to complete wastewater treatment in the sense
that they can remove very fine and discrete particles with sizes in the order of
molecules, atoms and ions.

6.3.1. Filtration
The object of filtration is to remove fine suspensions, with sizes exceeding one
micron, from effluents emanating in the biological stage. If this method is to be
applied, one must first determine: a) the number and size of filter units; b) the type
of filter to be employed; c) the configuration and characteristics of the filter beds; d)
the type of filter accessories - reverse washing; e) the operating factors of the filter
system; f) reactant requirements.
Number and size of filter units. The filter surface area is based on the maximum debit and filtrate output. The number filter units must be kept to a minimum in
order to reduce investment costs (constructions, pipes, etc.). When one unit is cut
out of service (for washing, for example), the other units must have the capacity to
take over the whole debit of water. The filter must be large enough to hold the
standard equipment of distribution, washing and drainage.
Selection of the filter type. There is a wide choice of available filters and filter
media - with continuous or discontinuous operation, conventional, with superficial
or deep bed. Filter media may be mono-layer, double or multi-medium, stratified or
non- stratified. Filters can work by gravitation or under pressure. Table 6.7 presents
some of the characteristics of the commercial filters.
Filter performances refer to the effluent quality. Thus, a 7 - 9 degree of
turbidity shall be reduced to less than 2 (16 - 23 mg/l) in the effluent. If this
parameter cannot be attained, chemical reactants are added.
Depending on the washing method, the filter material can be laid out stratified
or non-stratified. If water is the wash agent, the filter medium will be laid stratified
with the smaller particles at the surface. If air and water are used for washing, or in
fluidized media, stratification is not necessary. If sand is the medium, the specific
water debit will be 0.4 - 0.8 m3/m2 and minute, and the specific air flowrate will be
0.25 - 0.60 m3/m2 and minute. In the case of anthracite, the wash water flowrate
varies from 0.25 to 0.60 m3/m2 and minute, and the specific air flowrate from 6 to
20 m3/m2 and minute. Cleaning by air generates a more powerful washing action.
Air injection takes 3 - 4minutes.
Filter materials are characterized by their effective size (d10), coefficient of
uniformity, solubility, hardness, resistance to compression, granulometric curve.
Filter with superficial, stratified medium. The filter usually contains a
single-medium bed 0.3-m deep, made in two operating variants:
Filter with pulsating sand bed. The sand particles are maintained in suspension by an air diffuser placed at the surface of the bed. Air jets are introduced
periodically through the drain port (reverse washing), entraining the solids and
spreading them over the surface. When the pressure drop increases beyond the

278

Wastewater treatment. Technologies, installations and equipment

prescribed value, the filtration is stopped and the filter medium is washed by
reverse jets.
Filter with sand bed and straddling bridge. The filter is composed of several
cells filled with stratified sand. The system of reverse washing is mounted on a
bridge that travels over the cells washing them in turn. This washing method needs
no intervention and uses reduced debits of clean water for washing.
Table 6.7.
Design data for mono-medium type of filters
Characteristics
Superficial stratified bed
Sand - depth mm
- granule size mm
- coefficient of uniformity
- specific flowrate l/m2
Anthracite - depth mm
- granule size mm
- coefficient of uniformity
- specific flowrate l/m2
Conventional stratified bed
Sand - depth mm
- granule size mm
- coefficient of uniformity
- specific flowrate l/m2
Anthracite - depth mm
- granule size mm
- coefficient of uniformity
- specific flowrate l/m2
Deep, unstratified bed
Sand - depth mm
- granule size mm
- coefficient of uniformity
- specific flowrate l/m2
Anthracite depth mm
- granule size mm
- coefficient of uniformity
-specific flowrate l/m2

Variation range

Typical value

250300
0.350.60
1.21.6
81.5244.5
300500
0.81.5
1.31.8
81.5244.5

275
0.45
1.5
122.2
406
1.3
1.6
122

500762
0.40.8
1.21.6
81.5244.5
610920
0.82.0
1.31.8
82326

609
0.65
1.5
122
760
1.3
1.6
162

9151830
23
1.21.6
82410
9202140
24
1.31.8
82326

1220
2.5
1.5
205
1524
2.75
1.6
165

Filter with non-stratified mono-media bed. The filter is composed of a

single, 2 m deep bed of 2 - 3 mm granular medium that provides long periods of
operation. It can be used for both filtration and denitrification. Disadvantages: the
procedure requires a) a high degree of granular uniformity; b) high washing velocity
and consequently large wash water debit; c) high costs.
Another type of filter uses granular material of various sizes and a combined
air-water washing system, which permits removal of suspensions without fluidizing
the whole bed. The filtering medium is so arranged as to forms empty spaces of
various sizes with increasing retention capacity at the bottom of the bed.
Filter with stratified dual or multi-media bed. The dual media can be
combinations of anthracite and sand, charcoal and sand, resin and sand, resin and

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Methods and equipment for wastewater advanced treatment

anthracite. The multi-bed can be made up of: a) anthracite - sand - granite or

ilmenite; b) charcoal - anthracite - sand; c) spherical resin - anthracite - sand; d)
charcoal - sand - ilmenite. Typical values for specific flowrates used in fluidizing the
various layers are 1.79 - 1.96 m3/m2 min.
Table 6.8.
Processes of phosphorus removal
Technological operations
Conventional primary
- biological, with activated sludge
- filtration
- rotating biological contactor
Biological process - treatment in main stream
- treatment in auxiliary, separate stream
Combined process for nitrogen and phosphorous removal
Chemical process - precipitation with metal salt
- precipitation with lime
Physical processes filtration
- reverse osmosis
- adsorption on coal

Removal %
1020
1025
812
8...12
7090
7090
7090
7090
7090
2050
90100
1030

6.3.2. Reverse osmosis ultrafiltration

Osmosis is a flow process in which a constituent of an aqueous solution can
passes through a semi-permeable membrane while the other components cannot,
being blocked out. For saline solutions, for example, the membrane is permeable
to pure water but impermeable to salt. In this separation process the pure water
flows through the membrane due to the difference in concentration (osmotic
pressure). It will continue to pass through the membrane until the osmotic pressure
falls to a value equal to the flow resistance through the membrane. Reverse
osmosis is the phenomenon in which a solution, under the action of a pressure
difference, rises its concentration to a value exceeding the equilibrium value.

Fig. 6.12. Direct and reverse osmosis

a direct osmosis; b osmotic equilibrium; c reverse osmosis;
1 pure water; 2 salty water - multiphase medium

280

Wastewater treatment. Technologies, installations and equipment

The osmotic pressure appears in the physical phenomenon of a liquid flow

through a membrane dividing two liquid phases with different concentrations. The
pressure difference p between the two sides of the semi-permeable membrane is
pos = C R T [Pa], (Fig, 6.12), where C is the difference in concentration in
mol/m3, R = 8314 I/mol K - the constant of the perfect gases, T [K] - the absolute
temperature. In the case of seawater, which contains 35 g NaCl/l, at 15C, the
osmotic pressure is pos = 14,38 105 Pa This parameter is used for the calculation
in treatment processes based on reverse osmosis. The osmotic pressure of an
aqueous solution is a direct measure of the free energy of that solution. Solutions
with high concentrations of salt have a high osmotic pressure.
Reverse osmosis is a membrane process
based on forcing of water through a semi-permeable membrane by applying a pressure higher than the osmotic pressure of the solution.
Reverse osmosis or ultra-filtration permits the
removal of small, atomic and ionic particles of
the order of 1.10-5 - 1.10-3 microns. The factors
influencing the process are pressure, concentration, temperature and the nature of dissolved substances. Direct osmosis, or the process of rising concentration at the surface of the
membrane, creates an osmotic pressure that
Fig. 6.13. Flow through membrane
has to be overcome by a process of reverse
osmosis. This phenomenon is called the polarization of concentration of the membrane.
In reverse osmosis, the water flowrate Q is yielded by the relation
A
Q = K p (p pos ) K t , where Kp is the coefficient of permeability of water
s
through the membrane, S - the thickness of the membrane, p the of pressure
difference applied, Kt - the coefficient of temperature - expressing the influence of
temperature on viscosity. Since the flowrate grows with the temperature, at a
temperature elevation of 15C the flowrate will grow by 2.5 - 3.0%.
The osmotic installation (Fig. 6.14) consists of: a) a filtration equipment
designed to remove suspended solids and fats that might clog the membrane;
b) the batteries for reverse osmosis, constructed as pressure recipients; c) pumps
of low and high pressure; d) a turbine for energy recovery. The used water 1 is
introduced to the osmotic cell 5 by the low-pressure pump 2. The purified water
flows out through outlet 7 and the concentrated water passes through the energyrecovery turbine 5.
The vertical column of reverse osmosis (Fig. 6.15) is made up of a pipe (1),
membranes (2) held at a distance by a spacer (3). Wastewater (5) is distributed inbetween the two membranes. Because of high pressure, it is forced through the
membrane and through outlet 4.
The membrane must resist pressure differences of 200 - 1000 bars. It can be
made of: a) cellulose acetate- fabricated by the Loeb - Sourirajan method for the
desalination of sea water; b) nylon - for the treatment of wastewater effluents from
the paper and pulp industry and in the fabrication of fruit juice where it is used for
concentration.

Methods and equipment for wastewater advanced treatment

281

Fig. 6.14. Installation for reverse osmosis

1 - raw water; 2 - feed pump; 3 - filter; 4 - high pressure pump;
5 - recipient for osmosis; 6 - turbine for the recovery of hydraulic
energy; 7 - purified water

The acetate membrane incorporates a

thin film (slim) (0.2 - 1.0 microns) of very
dense polymer that will permits passage by
diffusion only. The nature of cellulose
diacetate in the membrane is such that it
de-structures the aqueous solution, letting
the pure water pass and blocking out the
salt. The method provides a high degree of
desalinization (98.5%) at a reasonable
flowrate. When organic macromolecules
(proteins) are separated from the water,
the mechanism is one of filtration and the
process is called ultra-filtration.
Reverse osmosis requires membranes with large surface area, easy to maintain and replace, while keeping the size of
the installation within reasonable limits.
Fig. 6.15. Osmotic column with
Commonly, the construction is modular
membranes
and may take the form of: a) plate modules; b) tubular modules (Fig. 6.15) and spiral modules (Roga-type). The multiple
modules of the installation work in parallel.

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Wastewater treatment. Technologies, installations and equipment

6.1. Processes for the removal of nitrogen compounds .................................................262

6.1.1. Nitrification .........................................................................................................262
6.1.2. Biological nitrification and denitrification..........................................................265
6.1.3. Methods of nitrification - denitrification with biological slim film attached
growth 271
6.1.4. Denitrification process in fluidized bed...............................................................273
6.1 5. Physical and chemical processes for nitrogen removal ......................................273
6.2. Methods for the removal of phosphorus .................................................................274
6.2.1. Biological procedures for the removal of phosphorous ......................................274
6.2.2. Phosphorus removal by metal salts and polymers...............................................276
6.3. Special procedures of treatment ..............................................................................277
6.3.1. Filtration .............................................................................................................277
6.3.2. Reverse osmosis ultrafiltration.........................................................................279