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260
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
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
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262
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
263
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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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
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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 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
267
268
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
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.
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.
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.
270
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)
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.
272
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
Specific load
kg BOD5 /m3 and day
0.1600.096
0.0980.048
0.2880.192
0.1920.096
273
274
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.
275
Unit
Food /biomass
Kg BOD5 /kg
VSS/day
Days
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
276
277
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
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
279
Removal %
1020
1025
812
8...12
7090
7090
7090
7090
7090
2050
90100
1030
280
281
282