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International Journal of Research in Engineering and Science (IJRES)
ISSN (Online): 2320-9364, ISSN (Print): 2320-9356
www.ijres.org Volume 1 Issue 7 ǁNov 2013 ǁPP.38-47
www.ijres.org 38 | Page
Performance of Fluidized Bed Biofilm Reactor
for Nitrate Removal
S. P. Burghate1
*, Dr. N. W. Ingole2
1*
Department of Civil Engineering, Government Polytechnic, Amravati, INDIA
2
Department of Civil Engineering, Prof. Ram Meghe Institute of Technology and Research, Badnera, INDIA
Abstract
Nitrate is present in the majority of water resources, and has reached serious level in many parts of the world,
which is responsible for environmental problems. Hence it is necessary to remove nitrate. Biological
denitrification provides the most economical means for nitrate removal. This paper represents the performance
of Fluidized Bed Biofilm Reactor (FBBR) using bone china fine granules as biofilm carrier media for biological
denitrification.
In this experimental work, the maximum average nitrogen removal efficiency of 93.71% at HRT of 30 minutes
and optimum efficiency of 88.13% at HRT of 10 minutes is observed. For nitrogen loading rates varying from
0.48 to 28.80 kg N m-3
d-1
, denitrification rates observed are 0.44 kg N m-3
d-1
to 17.26 kg N m-3
d-1
. Optimum
nitrogen loading rate and denitrification rate observed are 10.08 kg N m-3
d-1
and 8.88 kg N m-3
d-1
respectively.
The results justify the usefulness of FBBR for denitrification.
Keywords: Anoxic, Denitrification; Fluidized Bed Biofilm Reactor (FBBR); Methanol; Nitrate.
I. INTRODUCTION
Nitrate has become one of the key environmental issues because of its implications on human and
animal health. Nitrogen is a major constituent of the earth's atmosphere and occurs in many different gaseous
forms such as elemental nitrogen, nitrate and ammonia. While nitrate is a common nitrogenous compound due
to natural process of nitrogen cycle, anthropogenic sources have greatly increased the nitrate concentration,
particularly in groundwater [7]. The excessive applications of fertilizers, intensive exploitation of farms and the
significant contribution from industry have increased the nitrogen load discharged to receiving waterways [29,
40, 5]. Nitrate contamination of water resources is becoming a serious environmental problem worldwide [43,
21, 28, 6, 31]. A physico-chemical analysis study of groundwater in Sambhar lake city, Rajasthan, India was
carried out and researchers have found nitrate concentration levels upto 1100 mg l-1
[19]. After assessing the
water quality of Upper Lake, Bhopal (India), which supplies drinking water to 16 lakh populations, found nitrate
concentration as 150 – 720 mg l-1
[30]. In a case study carried out for water quality of water sources of Yavatmal
district, Maharashtra (India), found nitrate concentration in the range of 100 mg l-1
to 500 mg l-1
. Nitrate
concentration is above the permissible level of 45 mg l-1
in 11 states, covering 95 districts and 2 blocks of Delhi
[20]. Similar high concentratios of nitrate found in an investigation of nitrate content in ground and surface
waters in urban and rural areas [13]. Nitrate contamination of groundwater resources is becoming a problem in
Europe as well as in the United States and Canada. In many areas the nitrate concentration in groundwater has
reached serious levels exceeding the nominal limits of 10.0 mg l-1
as NO3
-
-N (nitrate nitrogen) set by the U.S.
Environmental Protection Agency or 50 mg l-1
as NO3
-
(nitrate) set by the World Health Organization, the
European Economic Community, and some former East European countries, e.g. Czechoslovakia. Concern over
increase in nitrate concentrations is very legitimate due to potential ill effects on health. The toxicity of nitrates
for humans is not clearly established. However, their consumption can cause infant methemoglobinemia (blue
baby syndrome). Reduction of nitrates into nitrites in saliva may contribute to the formation of nitrosoamines,
which are known carcinogens [33, 39, 14, 62, 64, 56]. Accumulation of various forms of nitrogen in surface and
ground waters can lead to adverse effects including depletion of dissolved oxygen (DO) in receiving waters,
eutrophication, ammonia toxicity to aquatic life, and public health problems related to the presence of nitrate in
drinking water supplies [61, 17, 11, 46, 45]. Nitrate can also cause anemia, oral cancer, cancer of colon, vascular
dementia and multiple sclerosis [40].
Till today, presence of nitrate in potable water had not been given serious attention in India. However
with the new dimensions of nitrate concentrations such as stomach cancer and other health problems, there is a
vital need to identify the areas of high nitrate waters and develop appropriate treatment. A survey of literature
yielded an abundance of information on the technical treatment to remove nitrate from water including ion
exchange, biological denitrification, chemical denitrification, catalytic denitrification, reverse osmosis and
electrodialysis [49]. Three methods show some potential for full-scale application: ion exchange, reverse
osmosis, and biological denitrification [33].
Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal
www.ijres.org 39 | Page
Nitrate from the contaminated water can be removed by ion exchange. Ion exchange is basically a
physical/chemical process which requires periodic regeneration to restore its exchange capacity and process
efficiency. It is known that periodic regeneration of exhausted resins with sodium chloride (NaCl) or sodium
bicarbonate (NaHCO3) results in a spent regenerant or brine waste containing high concentrations of nitrate-N,
NaCl and NaHCO3 [65]. Ion exchange is limited by two problems. The first is that a resin of high selectivity for
nitrates over ions that are commonly present in groundwater does not exist. The second problem involves
providing an adequate resin regenerant such that regenerant disposal does not become a problem itself [33].
The problem of reverse osmosis is that the membranes used generally do not exhibit high selectivity for nitrates.
The degree of salt rejection is directly related to the valency of the ions. That is why the reverse osmosis process
results in better removal of multivalent ions. Reverse osmosis results in the removal of many ionic species and
in a significant reduction in the mineral content of the water.
The most promising and versatile approach being studied is biological denitrification. This process has
been used for years in wastewater treatment. Biological denitrification is highly selective for nitrate removal.
The efficiency of the process is very high and can reach nearly 100%, which is not matched by any other
methods available for nitrate reduction. The potential bacterial contamination of treated water is the main
disadvantage. This risk is very legitimate and subsequent treatment and disinfection are required to meet current
drinking water standards [33]. Biological denitrification can be carried out in either fixed film or suspended
growth systems with the use of methanol or some equivalent carbon source. The FBBR is one of the methods,
which comes under the category of fixed film type of system. It is the recent method and can be used for
biological denitrification with great advantages.
The work presented in this paper is related to an experimental work carried out in the laboratory. A
setup of FBBR was established in the laboratory to study biological denitrification. The biofilm carrier media
used was sand which is easily available and economical. By considering the advantages of FBBR and sand
media, this study is carried out. The FBBR was run for several days to observe denitrification of synthetic
wastewater for various concentrations of NO3
-
-N, which vary from 10 mg l-1
to 100 mg l-1
. The results showed,
the FBBR has great potential for denitrification.
II. BIOLOGICAL DENITRIFICATION
Biological nitrification and denitrification is one of the most economical processes of nitrogen removal
from municipal wastewaters [27, 22, 47, 53]. Nitrate removal from wastewaters is commonly achieved by
employing the bacterial process of denitrification, in which nitrate is reduced to innocuous nitrogen gas (N2).
The process requires an electron donor to supply electrons (energy) to the bacteria [25, 59, 36, 23, 9, 60]. The
condition suitable for denitrification – absence of oxygen but presence of nitrate, is commonly referred as
anoxic. The biological denitrification process (dissimilation) involves the conversion of nitrate ions into
nitrogen gas by facultative heterotrophic bacteria. Anoxic conditions and an energy source are required for this.
Heterotrophic denitrifying bacteria require an organic carbon source for respiration and growth. Carbon source
plays an important role in biological nitrogen and phosphorus removal during the wastewater treatment [63]. A
wide variety of organic compounds have been used, such as methanol, ethanol, glucose, acetate, aspartate, or
formic acid as well as different industrial wastes including molasses, whey, distillery spillage, and sulfite waste
liquor. However, most of the published research regarding denitrification involves the use of methanol, ethanol,
and acetic acid [33]. The usefulness of methanol in the denitrification process is determined first of all by
economic considerations [15, 48]. Methanol is a very convenient carbon source for denitrification due to its high
solubility in water, high biodegradability and known stoichiometry [2, 12]. It is the most appropriate choice
because of its availability, low cost, favorable sludge production, low volatile organic compound (VOC)
emissions potential and lack of nitrogen and phosphorus.
If methanol is used as a carbon source, the stoichiometric relationships describing bacterial energy
reactions in two steps are written as equations 1 and 2 which give the overall (dissimilation) equation 3 [33, 65,
34] :
3 3 2 2 26NO 2CH OH 6NO 2CO 4H O 
 ï‚ź   (1)
2 3 2 2 26NO 3CH OH 3N 3CO 3H O 6OH 
 ï‚ź    (2)
3 3 2 2 26NO 5CH OH 3N 5CO 7H O 6OH 
 ï‚ź    (3)
Nitrate assimilation is generally expressed by equation 4:
3 3 2 5 7 2 23NO 14CH OH CO 4H 3C H NO 19H O
   ï‚ź  (4)
The cell formula C5H7NO2 suggested by Hoover and Porgess (Metcalf & Eddy, 2003) was used. The
“overall” (dissimilation + assimilation) process in nitrate-limiting conditions is described by McCarty’s equation
5 :
Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal
www.ijres.org 40 | Page
3 3 5 7 2 2 2 2NO 1.08CH OH H 0.065C H NO 0.467N 0.76CO 2.44H O 
  ï‚ź    (5)
Extension of Equation 5 to take also nitrite and oxygen, which often keep company with nitrate in the feed, into
account, gives to the empirical relation equation 6 weight basis [58].
 3 2 22.47( ) 1.53( ) 0.87 
    M gNO N gNO N g O (6)
The data found in the literature significantly differ from those in the above. In spite of 2.47, the value
of the coefficient in equation 6 was often found to be 2.65. and the suggested working value is 3.0 (g methanol)
/(g NO3
-
–N) removed); in spite of the coefficient 0.87 in equation 6, values as large as 1.1-1.2 have been found
as well [3].
This process of biological denitrification depends on environmental conditions such as oxygen content,
temperature and pH [16]. Alkalinity is produced in denitrification reactions and the pH is generally elevated,
instead of being depressed as in nitrification reactions. In contrast to nitrifying organisms, there has been less
concern about pH influences on denitrification rates. No significant effect of the denitrification rate has been
reported for pH between 7.0 and 8.0 [34].
2.1 Biological Denitrification System
Denitrification of a well nitrified effluent can be achieved by providing a zone in which the effluent is
brought into contact with a large biomass containing heterotrophic micro-organisms, in an anoxic environment;
and in the presence of a suitable exogenous carbon source. Complete denitrification appears feasible with the
use of methanol or some equivalent carbon source, in either attached growth (fixed film) or suspended growth
system.
III. FLUIDIZED BED BIOFILM REACTOR
The FBBR, the attached growth type of reactor (system), is a recent process innovation in wastewater
treatment, which utilizes small, fluidized media for cell immobilization and retention [37, 54]. Main application
of the FBBR is in the field of biological treatment of wastewater. Aerobic as well as anaerobic FBBRs have
received increasing attention for being an effective technology to treat water and wastewater [55, 51, 50, 35, 26,
38, 18, 52, 4, 42, 8]. Its most important features are - the fixation of microorganisms on the surface of small-
sized particles, leading to high content of active microorganisms and large surface area available for reaction
with the liquid; the high flow rate (low residence time) which can be achieved, leading to high degree of mixing
(decreased external mass transfer resistances) and to large reduction in size of the plant; and the removal of risk
of clogging [58].
The basic concept of the process consists of passing wastewater up through a packed bed of particles at
a velocity sufficient to impart motion to or fluidize the particles. As the flow of the wastewater passes upward
through the biological bed, very dense concentrations of organisms growing on the surface of the bed particles
consume the biodegradable waste contaminants in the liquid. Figure 1 is a schematic of the basic unit of the
process, showing the entire FBBR with the wastewater flowing upwards through the bed, fluidizing the particles
in the liquid. Above the bed is a clear water zone wherein the particles separate from the liquid.
From a biological point of view, the attached microorganisms on the suspended particles may include any of the
aerobic, facultative, or anaerobic organisms typically found in trickling filters and suspended growth type of
treatment systems. The predominating species would depend entirely on the waste contaminant being consumed
and whether an aerobic or anaerobic environment is maintained, as well as other factors that affect biological
growth.
Fluidized beds combine the best features of activated sludge and trickling filtration into one process.
Offering a fixed film and a large surface area, these systems offer the stability and ease of operation of the
trickling filter as well as the greater operating efficiency of the activated sludge process. More importantly,
treatment is accomplished in significantly less space and time, which can be translated into less cost than
conventional treatment. The primary reason for this savings in space, cost, and treatment time is that the
measured concentration of active biomass in the fluidized bed system reported is in the order of 8,000 mg l-1
–
40,000 mg l-1
, which is usually greater than conventional treatment systems such as the complete-mix activated
sludge process in which the MLSS (Mixed Liquor Suspended Solids) ranges between 3,000 mg l-1
– 6,000 mg l-1
or the pure oxygen systems where the MLSS ranges from 6,000 mg l-1
– 8,000 mg l-1
[57, 42]. The reason for
this is that the available surface area per unit of volume of reactor for biological growth in the fluidized bed
system is much greater than either trickling filters or rotating biological contactors. This area is estimated to be
about 3,290 m2
m-3
, which is far greater than that of trickling filter (82.25 m2
m-3
) or of the rotating disc (164.5
m2
m-3
). Fluidized beds with attached microbial growth on carrier particles have been found to be extremely
efficient for biodegradation of liquid waste. Both aerobic as well as anaerobic degradation can effectively be
obtained. In capital cost including land, tanks, pumps, clarifiers and solid separators, works out at 1/4th
the cost
of that for the conventional suspended growth process. The operating cost is slightly lower for the same capacity
Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal
www.ijres.org 41 | Page
[32]. In anaerobic FBBR, biomass concentrations exceeding 30,000 mg l-1
have been reported and organic
removal efficiencies of 80 percent were achieved at loadings of 4 kg COD m-3
d-1
on dilute wastewaters [10].
The advantages of FBBR can be summarized as follows. First, higher biomass concentration can be maintained
in the process; hence the system has more metabolic activities, compared to that of suspended growth system.
Second, the presence of longer food chains in biofilm with abundant microbial species and can provide stability,
long retention time of microbes and much less surplus sludge. Third, the coexistence of aerobic and anoxic
zones within the biomass film could provide an opportunity for simultaneous nitrification and denitrification to
occur. Fourth, the biofilm processes are less sensitive to the toxic condition and other adverse operational
conditions, thus making them easy to operate and maintain. Finally, problems caused by poor settling of sludge
and sludge bulking would not be encountered during operation [41].
IV. MATERIALS AND METHODS
4.1 Fluidized Bed Biofilm Reactor (Denitrifying Unit)
The experimental setup used for this study is shown in Figure 1. Its main part is the 1.22 l reactor made
of Plexiglas tube (0.036 m diameter, 1.20 m long), which is fixed to a steel stand. It is filled with uniform bone
china fine granules as a biofilm carrier to a settled depth of 0.30 m. At the bottom, a small closed influent tank
of 6 l capacity is provided to which pump is fitted which supplies the influent to the reactor. At the top of the
reactor an outlet pipe (tube) is joined which collects the effluent from the reactor and discharge again into
influent tank. At the inlet of the reactor, a regulator cock is provided to regulate the flow as well as fluidization
of media in the reactor. Fine screens are provided at both the ends (bottom and top end) of the reactor to avoid
escape of media from the reactor and also to distribute the flow uniformly in the reactor.
pH, temperature, alkalinity, COD and NO3
-
N concentrations were systematically recorded at the end of each
run.
4.2 Biofilm Carrier Media
Various materials have been tried by researchers as biofilm carrier media. e.g. sand, glass beads,
activated carbon, cement ball [18], plastic, etc. In this study bone china fine granules were used as biofilm
carrier media. It is prepared by crushing and sieving waste bone china (crockery) material. The characteristics
found after performing particle size distribution of bone china fine granules were – Effective size (D10) 0.129
mm, Coefficient of Uniformity Cu (D60/D10) 3.648, Coefficient of curvature or gradation Cc ((D30)2
/(D60*D10))
0.019, and Specific gravity 2.26.
4.3 Feed
A synthetic medium (synthetic wastewater) was prepared using deionized water in addition to the other
chemicals. Potassium nitrate (KNO3) was added as the nitrogen source at different varying concentrations of
NO3
-
-N in mg l-1
. PO4
3-
(as Na2HPO4.12H2O and KH2PO4) both as P source and medium buffering agent. Trace
mineral constituents essential to the bacterial growth added per liter were : 0.85 mg FeSO4.7H2O, 0.25 mg
Na2MoO4.2H2O, 0.157 mg MnSO4.7H2O and 33 mg NaHCO3. Sodium sulfite and Cobalt chloride were added at
concentrations of 20 and 0.55 mg l-1
respectively, to reduce the oxygen concentration to below 0.5 mg l-1
to
ensure anoxic conditions in the reactors [42]. The Methanol was used as carbon source. The concentration of
NO3
-
- N and methanol in the medium was varied at different stages of the study to maintain (methanol/NO3
-
-N)
ratio.
4.4 Operation of a Fluidized Bed Biofilm Reactor
Figure 1 shows schematic diagram of the FBBR which was operated daily for denitrification, nearly for
a year. The reactor was inoculated with domestic wastewater and run by feeding synthetic medium for 15 days.
After getting proper results, the reactor was operated for 75 days to find out optimum methanol/NO3
-
- N ratio.
For this, reactor was run for 15 days each for each methanol/NO3
-
- N ratio of 2.25, 2.50, 2.75, 3.00 and 3.25.
Average NO3
-
- N removal efficiency obtained was 67.95%, 78.96%, 84.55%, 89.88% and 86.63% for
methanol/NO3
-
- N ratios 2.25, 2.50, 2.75, 3.00 and 3.25 respectively. Hence, the ratio of 3.00 was finalized for
the present study.
Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal
www.ijres.org 42 | Page
Figure 1. Experimental Setup of Fluidized Bed Biofilm Reactor.
For Experimental work, by maintaining constant methanol/NO3
-
- N ratio as 3.00, the synthetic
wastewater samples were prepared for varying concentration of NO3
-
-N of 10.00 mg l-1
, 20.00 mg l-1
, 30.00 mg
l-1
, 40.00 mg l-1
, 50.00 mg l-1
, 60.00 mg l-1
, 70.00 mg l-1
, 80.00 mg l-1
, 90.00 mg l-1
and 100.00 mg l-1
. For these
each concentrations of NO3
-
-N, the reactor was run for 10 days and various characteristics of influent and
effluent were measured at the end of each run (i.e. hydraulic retention time (HRT) of 5 minutes, 10 minutes, 15
minutes, 20 minutes, 25 minutes, 30 minutes). The characteristics measured were temperature, pH, alkalinity,
COD and NO3
-
-N.
4.5 Analytical Methods
Samples were collected from the FBBR at regular intervals. These samples were tested for various
characteristics. pH was measured by digital pH Meter. Alkalinity was determined by titration method according
to APHA [1]. COD was measured by reflux method according to APHA [1]. NO3
-
-N was measured by UV-
Spectrophotometer (Schimadzu make, Model – UV 1650).
V. RESULTS AND DISCUSSION
The experimental denitrification reactor was operated for 10 different concentrations and readings were
recorded at HRT of 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, and 30 minutes. The NO3
-
-N
removal was determined on the basis of the results of analysis of medium entering and leaving the reactor for
methanol/ NO3
-
-N ratio of 3.00. Average NO3
-
-N removal Efficiency was found to be 60.60%, 86.86%, 88.77%,
90.72%, 91.75% and 92.26% for HRT of 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, and 30
minutes respectively. The results are shown graphically in Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6, and Fig. 7.
In this study, it was found that, NO3
-
-N removal efficiency was in the increasing order for the
increasing concentration of NO3
-
-N up to 70 mg l-1
, after this trend was declining. NO3
-
-N removal efficiency for
hydraulic retention time of 30 minutes for NO3
-
-N concentration of 10 mg l-1
, 20 mg l-1
, 30 mg l-1
, 40 mg l-1
, 50
mg l-1
, 60 mg l-1
and 70 mg l-1
was 91.52%, 92.17%, 92.10%, 92.45%, 92.72%, 92.64% and 93.71%. And
NO3
-
-N removal efficiency after 30 minutes for NO3
-
-N concentration of 80 mg l-1
, 90 mg l-1
and 100 mg l-1
was
92.19%, 91.60%, 91.51%. Fig. 8 shows graphical representation of NO3
-
-N removal % for different HRTs.
From the Figure, it was observed that, as the concentration of NO3
-
-N increases in the wastewater sample (i.e.
from 10.00 mg l-1
to 70.00 mg l-1
) there was a gradual increase in NO3
-
-N removal. But after this there was a
slight decrease in NO3
-
-N removal rate. This might be due to less concentration of available NO3
-
-N present in
the wastewater.
Fig. 9 shows the graphical representation of NO3
-
-N removal % for wastewater containing varying
concentrations of NO3
-
-N at different HRTs. From the readings and figures, it was observed that most of the
NO3
-
-N was removed at HRT of 10 minutes. There is a very little difference between NO3
-
-N removal % at HRT
of 10 and 30 minutes. Thus HRT of 10 minutes can be considered as optimum condition.
Inlet
Tank
Glass Tube
(0.036 M Dia,
1.20 M long)
Fluidized
Media
Regulator
Cock
Pump
Inlet
Pipe
Outlet Pipe
Denitrifying
Reactor
Figure 1 : Experimental Setup of
Fluidized Bed Biofilm Reactor
Synthetic
Wastewater
Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal
www.ijres.org 43 | Page
In the present study, the nitrogen loading rates varied from 0.48 kg N m-3
d-1
to 28.80 kg N m-3
d-1
. For these
nitrogen loading rates, denitrification rates observed vary from 0.44 kg N m-3
d-1
to 17.26 kg N m-3
d-1
. But
optimum (at maximum NO3
-
-N removal efficiency), nitrogen loading rate and denitrification rate observed were
10.08 kg N m-3
d-1
and 8.88 kg N m-3
d-1
respectively. Rezaee et al. [44], in their study to investigate technical
feasibility of biological nitrate removal in a packed bed reactor using microbial cellulose as biopolymer carrier,
got denitrification rate of 4.7 kg NO3
-
-N m-3
d-1
for loading rate of 5.64 kg NO3
-
-N m-3
d-1
. The biofilm reactors
give high nitrate removal rate from 3.1 - 4.4 kg NO3
-
-N m-3
d-3
to 10 – 12 kg NO3
-
-N m-3
d-3
[25]. Rabah [42],
presented the results of his study in comparison with the other studies in which fluidized bed reactors were
reportedly used with methanol as the carbon source (Table 1). Results found by Rabah [42] were found to be in
agreement with the results obtained in this research.
54
56
58
60
62
Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10
NO3
--NRemoval(%)
Day
Fig. 2 : NO3
--N Removal after 5 Minutes (HRT)
for Different Concentrations of NO3
--N
NO3--N = 10 mg/l
NO3--N = 20 mg/l
NO3--N = 30 mg/l
NO3--N = 40 mg/l
NO3--N = 50 mg/l
NO3--N = 60 mg/l
NO3--N = 70 mg/l
NO3--N = 80 mg/l
NO3--N = 90 mg/l
NO3--N = 100 mg/l
82
84
86
88
Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10
NO3
--NRemoval(%)
Day
Fig. 3 : NO3
--N Removal after 10 Minutes
(HRT) for Different Concentrations of NO3
--N
NO3--N = 10 mg/l
NO3--N = 20 mg/l
NO3--N = 30 mg/l
NO3--N = 40 mg/l
NO3--N = 50 mg/l
NO3--N = 60 mg/l
NO3--N = 70 mg/l
NO3--N = 80 mg/l
NO3--N = 90 mg/l
NO3--N = 100 mg/l
86
87
88
89
90
91
92
Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10
NO3
--NRemoval(%)
Day
Fig. 4 : NO3
--N Removal after 15 Minutes
(HRT) for Different Concentrations of NO3
--N
NO3--N = 10 mg/l NO3--N = 20 mg/l
NO3--N = 30 mg/l NO3--N = 40 mg/l
NO3--N = 50 mg/l NO3--N = 60 mg/l
NO3--N = 70 mg/l NO3--N = 80 mg/l
NO3--N = 90 mg/l NO3--N = 100 mg/l
86
87
88
89
90
91
92
Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10
NO3
--NRemoval(%)
Day
Fig. 5 : NO3
--N Removal after 20 Minutes
(HRT) for Different Concentrations of NO3
--N
NO3--N = 10 mg/l
NO3--N = 20 mg/l
NO3--N = 30 mg/l
NO3--N = 40 mg/l
NO3--N = 50 mg/l
NO3--N = 60 mg/l
NO3--N = 70 mg/l
NO3--N = 80 mg/l
NO3--N = 90 mg/l
NO3--N = 100 mg/l
Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal
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89
90
91
92
93
94
Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10
NO3
--NRemoval(%)
Day
Fig. 6 : NO3
--N Removal after 25 Minutes
(HRT) for Different Concentrations of NO3
--N
NO3--N = 10 mg/l NO3--N = 20 mg/l
NO3--N = 30 mg/l NO3--N = 40 mg/l
NO3--N = 50 mg/l NO3--N = 60 mg/l
NO3--N = 70 mg/l NO3--N = 80 mg/l
NO3--N = 90 mg/l NO3--N = 100 mg/l
89
90
91
92
93
94
Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10
NO3
--NRemoval(%)
Day
Fig. 7 : NO3
--N Removal after 30 Minutes
(HRT) for Different Concentrations of NO3
--N
NO3--N = 10 mg/l
NO3--N = 20 mg/l
NO3--N = 30 mg/l
NO3--N = 40 mg/l
NO3--N = 50 mg/l
NO3--N = 60 mg/l
NO3--N = 70 mg/l
NO3--N = 80 mg/l
NO3--N = 90 mg/l
NO3--N = 100 mg/l
58
63
68
73
78
83
88
93
10 20 30 40 50 60 70 80 90 100
NO3
--NAxisRemoval(%)
NO3
-- N Concentration mg l-1
Fig. 8 : NO3
-- N Removal (%) for Different
HRTs for Different Concentrations of NO3
-- N
HRT = 05 Minutes HRT = 10 Minutes
HRT = 15 Minutes HRT = 20 Minutes
HRT = 25 Minutes HRT = 30 Minutes
58
63
68
73
78
83
88
93
5 10 15 20 25 30
NO3
--NRemoval(%)
Hydraulic Retention Time in Minutes
Fig. 9 : NO3
--N Removal for Different
Concentrations of NO3
--N at Different HRTs
Nitrate N = 10 mg/l
Nitrate N = 20 mg/l
Nitrate N = 30 mg/l
Nitrate N = 40 mg/l
Nitrate N = 50 mg/l
Nitrate N = 60 mg/l
Nitrate N = 70 mg/l
Nitrate N = 80 mg/l
Nitrate N = 90 mg/l
Nitrate N = 100 mg/l
Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal
www.ijres.org 45 | Page
Table 1: Comparison of some studies on denitrification using fluidized bed reactors
Form of
Nitrogen
Temperature
(0
C)
Concentration of
Nitrogen (mg l-1
)
Denitrification Rate
(kg N m-3
d-1
)
References
NO3
–
N 18-23 5 – 100 5.4 – 20.70 Jeris and Owens (1975).
NO3
–
N - 6.6 – 30 0.69 – 3.28 Hermanwicz and Cheng (1990).
NO3
–
N 30 15 – 300 3.23 – 18.70 Hirata and Meutia (1996).
NO3
–
N 20 20 3.5 MacDonald (1990).
NO3
–
N - 676 – 1500 11.8 – 17.7 Chen et al (1996).
NO3
–
N 23 1000 12 Rabah Fahid K. J., et al, (2004).
NO3
–
N 24.5 – 40.5 10 – 100
0.44 – 17.26
(Optimum 8.88)
This Study
Courtesy: Rabah [42].
Heterotrophic denitrification causes a release of hydroxyl ions and raises alkalinity. Each mg of nitrate-
N reduced to N2 causes an alkalinity increase of 3.57 mg CaCO3 [45]. In this study, average g of Alkali
produced per g of NO3
-
-N removed was found to be 3.60 which is in agreement with the value found in
literature. As alkalinity is produced, there is a rise in pH. pH of the influent was in the range of 6.56 – 7.15 and
that of effluent observed was in the range of 6.76 – 8.06.
The denitrification intensity depends on carbon availability. The carbon to nitrogen ratio in the
biological reactor influent should be high enough to denitrify all nitrates arisen in the nitrification process.
Komorowska-Kaufman [24], mentioned in his paper, many researchers’ work revealed the g ∆COD/g ∆N ratio
as 3.5 – 4.5. In the present study, based on all the results, average g of COD consumed per g of NO3
-
-N
removed is found to be 3.70. This is in confirmation with the results obtained by many researchers.
VI. CONCLUSION
The results of the investigation, demonstrated that the trend of the removal of NO3
-
-N is quite high up
to hydraulic retention time of 10 minutes. An average removal rate at this HRT observed was 88.13%. Also on
the initial NO3
-
-N concentration basis, it was observed that for initial concentrations upto 70 mg l-1
, the NO3
-
-N
removal rate was in increasing order but for higher concentrations, the trend was slightly declining. The
efficiency can be improved by using special culture of denitrifying microorganisms in the FBBR.
The result of this study demonstrated conclusively that FBBR with bone china fine granules as a biofilm carrier
media can be used with great advantages for denitrification.
This study provides the justification for the recommendation of FBBR for denitrification by many researchers.
VII. ACKNOWLEDGEMENT
We are grateful to Principal, Government College of Engineering, Amravati and Incharges of Environmental
Engineering Laboratory at Government College of Engineering, Amravati Prof. Mokadam A. M., Prof. Gulhane
M. L. and Prof. Rai R. K. for giving permission to carry out laboratory work in their Institute and their guidance
and timely help. We are also thankful to Prof. D. N. Shingade, Principal, Government Polytechnic, Amravati,
for giving permission to carry out the present study.
S. P. Burghate received M. E. (Environmental Engineering) from Government College of Engineering,
Amravati, Maharashtra, India in 1992. He is Lecturer in the Department of Civil Engineering, at Government
Polytechnic, Amravati, Maharashtra, India. His research interests include treatment of water and wastewater,
solid waste management. He has published 5 papers in National and International journals. He has also
presented 6 research articles in national and international conferences. He is a Life Member of professional
bodies like, IE (India), ISTE (India), and IWWA.
Dr. N. W. Ingole is a Professor and Head in the Department of Civil Engineering, Prof. Ram Meghe Institute of
Technology and Research, Badnera, Amravati, Maharashtra, India. He has more than 24 years of experience in
teaching and research. His current area of research includes treatment of water and wastewater, solid waste
management, Quality Engineering, Neural Networks, Optimization and Simulation. He has published more than
63 papers in refereed National and International journals of repute. He has also presented more than 10 research
articles in national and international conferences. He has written a book titled “Environmental Chemistry and
Pollution Control”. He is life member of National and International Professional Societies, Fellow of Institution
of Engineers (India). He is recipient of many National and International awards. He has also got “Promising
Engineering Teacher in Engineering Colleges Award”. He is currently dealing with few projects sponsored by
government of India.
Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal
www.ijres.org 46 | Page
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Performance of Fluidized Bed Biofilm Reactor for Nitrate Removal

  • 1. International Journal of Research in Engineering and Science (IJRES) ISSN (Online): 2320-9364, ISSN (Print): 2320-9356 www.ijres.org Volume 1 Issue 7 ǁNov 2013 ǁPP.38-47 www.ijres.org 38 | Page Performance of Fluidized Bed Biofilm Reactor for Nitrate Removal S. P. Burghate1 *, Dr. N. W. Ingole2 1* Department of Civil Engineering, Government Polytechnic, Amravati, INDIA 2 Department of Civil Engineering, Prof. Ram Meghe Institute of Technology and Research, Badnera, INDIA Abstract Nitrate is present in the majority of water resources, and has reached serious level in many parts of the world, which is responsible for environmental problems. Hence it is necessary to remove nitrate. Biological denitrification provides the most economical means for nitrate removal. This paper represents the performance of Fluidized Bed Biofilm Reactor (FBBR) using bone china fine granules as biofilm carrier media for biological denitrification. In this experimental work, the maximum average nitrogen removal efficiency of 93.71% at HRT of 30 minutes and optimum efficiency of 88.13% at HRT of 10 minutes is observed. For nitrogen loading rates varying from 0.48 to 28.80 kg N m-3 d-1 , denitrification rates observed are 0.44 kg N m-3 d-1 to 17.26 kg N m-3 d-1 . Optimum nitrogen loading rate and denitrification rate observed are 10.08 kg N m-3 d-1 and 8.88 kg N m-3 d-1 respectively. The results justify the usefulness of FBBR for denitrification. Keywords: Anoxic, Denitrification; Fluidized Bed Biofilm Reactor (FBBR); Methanol; Nitrate. I. INTRODUCTION Nitrate has become one of the key environmental issues because of its implications on human and animal health. Nitrogen is a major constituent of the earth's atmosphere and occurs in many different gaseous forms such as elemental nitrogen, nitrate and ammonia. While nitrate is a common nitrogenous compound due to natural process of nitrogen cycle, anthropogenic sources have greatly increased the nitrate concentration, particularly in groundwater [7]. The excessive applications of fertilizers, intensive exploitation of farms and the significant contribution from industry have increased the nitrogen load discharged to receiving waterways [29, 40, 5]. Nitrate contamination of water resources is becoming a serious environmental problem worldwide [43, 21, 28, 6, 31]. A physico-chemical analysis study of groundwater in Sambhar lake city, Rajasthan, India was carried out and researchers have found nitrate concentration levels upto 1100 mg l-1 [19]. After assessing the water quality of Upper Lake, Bhopal (India), which supplies drinking water to 16 lakh populations, found nitrate concentration as 150 – 720 mg l-1 [30]. In a case study carried out for water quality of water sources of Yavatmal district, Maharashtra (India), found nitrate concentration in the range of 100 mg l-1 to 500 mg l-1 . Nitrate concentration is above the permissible level of 45 mg l-1 in 11 states, covering 95 districts and 2 blocks of Delhi [20]. Similar high concentratios of nitrate found in an investigation of nitrate content in ground and surface waters in urban and rural areas [13]. Nitrate contamination of groundwater resources is becoming a problem in Europe as well as in the United States and Canada. In many areas the nitrate concentration in groundwater has reached serious levels exceeding the nominal limits of 10.0 mg l-1 as NO3 - -N (nitrate nitrogen) set by the U.S. Environmental Protection Agency or 50 mg l-1 as NO3 - (nitrate) set by the World Health Organization, the European Economic Community, and some former East European countries, e.g. Czechoslovakia. Concern over increase in nitrate concentrations is very legitimate due to potential ill effects on health. The toxicity of nitrates for humans is not clearly established. However, their consumption can cause infant methemoglobinemia (blue baby syndrome). Reduction of nitrates into nitrites in saliva may contribute to the formation of nitrosoamines, which are known carcinogens [33, 39, 14, 62, 64, 56]. Accumulation of various forms of nitrogen in surface and ground waters can lead to adverse effects including depletion of dissolved oxygen (DO) in receiving waters, eutrophication, ammonia toxicity to aquatic life, and public health problems related to the presence of nitrate in drinking water supplies [61, 17, 11, 46, 45]. Nitrate can also cause anemia, oral cancer, cancer of colon, vascular dementia and multiple sclerosis [40]. Till today, presence of nitrate in potable water had not been given serious attention in India. However with the new dimensions of nitrate concentrations such as stomach cancer and other health problems, there is a vital need to identify the areas of high nitrate waters and develop appropriate treatment. A survey of literature yielded an abundance of information on the technical treatment to remove nitrate from water including ion exchange, biological denitrification, chemical denitrification, catalytic denitrification, reverse osmosis and electrodialysis [49]. Three methods show some potential for full-scale application: ion exchange, reverse osmosis, and biological denitrification [33].
  • 2. Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal www.ijres.org 39 | Page Nitrate from the contaminated water can be removed by ion exchange. Ion exchange is basically a physical/chemical process which requires periodic regeneration to restore its exchange capacity and process efficiency. It is known that periodic regeneration of exhausted resins with sodium chloride (NaCl) or sodium bicarbonate (NaHCO3) results in a spent regenerant or brine waste containing high concentrations of nitrate-N, NaCl and NaHCO3 [65]. Ion exchange is limited by two problems. The first is that a resin of high selectivity for nitrates over ions that are commonly present in groundwater does not exist. The second problem involves providing an adequate resin regenerant such that regenerant disposal does not become a problem itself [33]. The problem of reverse osmosis is that the membranes used generally do not exhibit high selectivity for nitrates. The degree of salt rejection is directly related to the valency of the ions. That is why the reverse osmosis process results in better removal of multivalent ions. Reverse osmosis results in the removal of many ionic species and in a significant reduction in the mineral content of the water. The most promising and versatile approach being studied is biological denitrification. This process has been used for years in wastewater treatment. Biological denitrification is highly selective for nitrate removal. The efficiency of the process is very high and can reach nearly 100%, which is not matched by any other methods available for nitrate reduction. The potential bacterial contamination of treated water is the main disadvantage. This risk is very legitimate and subsequent treatment and disinfection are required to meet current drinking water standards [33]. Biological denitrification can be carried out in either fixed film or suspended growth systems with the use of methanol or some equivalent carbon source. The FBBR is one of the methods, which comes under the category of fixed film type of system. It is the recent method and can be used for biological denitrification with great advantages. The work presented in this paper is related to an experimental work carried out in the laboratory. A setup of FBBR was established in the laboratory to study biological denitrification. The biofilm carrier media used was sand which is easily available and economical. By considering the advantages of FBBR and sand media, this study is carried out. The FBBR was run for several days to observe denitrification of synthetic wastewater for various concentrations of NO3 - -N, which vary from 10 mg l-1 to 100 mg l-1 . The results showed, the FBBR has great potential for denitrification. II. BIOLOGICAL DENITRIFICATION Biological nitrification and denitrification is one of the most economical processes of nitrogen removal from municipal wastewaters [27, 22, 47, 53]. Nitrate removal from wastewaters is commonly achieved by employing the bacterial process of denitrification, in which nitrate is reduced to innocuous nitrogen gas (N2). The process requires an electron donor to supply electrons (energy) to the bacteria [25, 59, 36, 23, 9, 60]. The condition suitable for denitrification – absence of oxygen but presence of nitrate, is commonly referred as anoxic. The biological denitrification process (dissimilation) involves the conversion of nitrate ions into nitrogen gas by facultative heterotrophic bacteria. Anoxic conditions and an energy source are required for this. Heterotrophic denitrifying bacteria require an organic carbon source for respiration and growth. Carbon source plays an important role in biological nitrogen and phosphorus removal during the wastewater treatment [63]. A wide variety of organic compounds have been used, such as methanol, ethanol, glucose, acetate, aspartate, or formic acid as well as different industrial wastes including molasses, whey, distillery spillage, and sulfite waste liquor. However, most of the published research regarding denitrification involves the use of methanol, ethanol, and acetic acid [33]. The usefulness of methanol in the denitrification process is determined first of all by economic considerations [15, 48]. Methanol is a very convenient carbon source for denitrification due to its high solubility in water, high biodegradability and known stoichiometry [2, 12]. It is the most appropriate choice because of its availability, low cost, favorable sludge production, low volatile organic compound (VOC) emissions potential and lack of nitrogen and phosphorus. If methanol is used as a carbon source, the stoichiometric relationships describing bacterial energy reactions in two steps are written as equations 1 and 2 which give the overall (dissimilation) equation 3 [33, 65, 34] : 3 3 2 2 26NO 2CH OH 6NO 2CO 4H O   ï‚ź   (1) 2 3 2 2 26NO 3CH OH 3N 3CO 3H O 6OH   ï‚ź    (2) 3 3 2 2 26NO 5CH OH 3N 5CO 7H O 6OH   ï‚ź    (3) Nitrate assimilation is generally expressed by equation 4: 3 3 2 5 7 2 23NO 14CH OH CO 4H 3C H NO 19H O    ï‚ź  (4) The cell formula C5H7NO2 suggested by Hoover and Porgess (Metcalf & Eddy, 2003) was used. The “overall” (dissimilation + assimilation) process in nitrate-limiting conditions is described by McCarty’s equation 5 :
  • 3. Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal www.ijres.org 40 | Page 3 3 5 7 2 2 2 2NO 1.08CH OH H 0.065C H NO 0.467N 0.76CO 2.44H O    ï‚ź    (5) Extension of Equation 5 to take also nitrite and oxygen, which often keep company with nitrate in the feed, into account, gives to the empirical relation equation 6 weight basis [58].  3 2 22.47( ) 1.53( ) 0.87      M gNO N gNO N g O (6) The data found in the literature significantly differ from those in the above. In spite of 2.47, the value of the coefficient in equation 6 was often found to be 2.65. and the suggested working value is 3.0 (g methanol) /(g NO3 - –N) removed); in spite of the coefficient 0.87 in equation 6, values as large as 1.1-1.2 have been found as well [3]. This process of biological denitrification depends on environmental conditions such as oxygen content, temperature and pH [16]. Alkalinity is produced in denitrification reactions and the pH is generally elevated, instead of being depressed as in nitrification reactions. In contrast to nitrifying organisms, there has been less concern about pH influences on denitrification rates. No significant effect of the denitrification rate has been reported for pH between 7.0 and 8.0 [34]. 2.1 Biological Denitrification System Denitrification of a well nitrified effluent can be achieved by providing a zone in which the effluent is brought into contact with a large biomass containing heterotrophic micro-organisms, in an anoxic environment; and in the presence of a suitable exogenous carbon source. Complete denitrification appears feasible with the use of methanol or some equivalent carbon source, in either attached growth (fixed film) or suspended growth system. III. FLUIDIZED BED BIOFILM REACTOR The FBBR, the attached growth type of reactor (system), is a recent process innovation in wastewater treatment, which utilizes small, fluidized media for cell immobilization and retention [37, 54]. Main application of the FBBR is in the field of biological treatment of wastewater. Aerobic as well as anaerobic FBBRs have received increasing attention for being an effective technology to treat water and wastewater [55, 51, 50, 35, 26, 38, 18, 52, 4, 42, 8]. Its most important features are - the fixation of microorganisms on the surface of small- sized particles, leading to high content of active microorganisms and large surface area available for reaction with the liquid; the high flow rate (low residence time) which can be achieved, leading to high degree of mixing (decreased external mass transfer resistances) and to large reduction in size of the plant; and the removal of risk of clogging [58]. The basic concept of the process consists of passing wastewater up through a packed bed of particles at a velocity sufficient to impart motion to or fluidize the particles. As the flow of the wastewater passes upward through the biological bed, very dense concentrations of organisms growing on the surface of the bed particles consume the biodegradable waste contaminants in the liquid. Figure 1 is a schematic of the basic unit of the process, showing the entire FBBR with the wastewater flowing upwards through the bed, fluidizing the particles in the liquid. Above the bed is a clear water zone wherein the particles separate from the liquid. From a biological point of view, the attached microorganisms on the suspended particles may include any of the aerobic, facultative, or anaerobic organisms typically found in trickling filters and suspended growth type of treatment systems. The predominating species would depend entirely on the waste contaminant being consumed and whether an aerobic or anaerobic environment is maintained, as well as other factors that affect biological growth. Fluidized beds combine the best features of activated sludge and trickling filtration into one process. Offering a fixed film and a large surface area, these systems offer the stability and ease of operation of the trickling filter as well as the greater operating efficiency of the activated sludge process. More importantly, treatment is accomplished in significantly less space and time, which can be translated into less cost than conventional treatment. The primary reason for this savings in space, cost, and treatment time is that the measured concentration of active biomass in the fluidized bed system reported is in the order of 8,000 mg l-1 – 40,000 mg l-1 , which is usually greater than conventional treatment systems such as the complete-mix activated sludge process in which the MLSS (Mixed Liquor Suspended Solids) ranges between 3,000 mg l-1 – 6,000 mg l-1 or the pure oxygen systems where the MLSS ranges from 6,000 mg l-1 – 8,000 mg l-1 [57, 42]. The reason for this is that the available surface area per unit of volume of reactor for biological growth in the fluidized bed system is much greater than either trickling filters or rotating biological contactors. This area is estimated to be about 3,290 m2 m-3 , which is far greater than that of trickling filter (82.25 m2 m-3 ) or of the rotating disc (164.5 m2 m-3 ). Fluidized beds with attached microbial growth on carrier particles have been found to be extremely efficient for biodegradation of liquid waste. Both aerobic as well as anaerobic degradation can effectively be obtained. In capital cost including land, tanks, pumps, clarifiers and solid separators, works out at 1/4th the cost of that for the conventional suspended growth process. The operating cost is slightly lower for the same capacity
  • 4. Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal www.ijres.org 41 | Page [32]. In anaerobic FBBR, biomass concentrations exceeding 30,000 mg l-1 have been reported and organic removal efficiencies of 80 percent were achieved at loadings of 4 kg COD m-3 d-1 on dilute wastewaters [10]. The advantages of FBBR can be summarized as follows. First, higher biomass concentration can be maintained in the process; hence the system has more metabolic activities, compared to that of suspended growth system. Second, the presence of longer food chains in biofilm with abundant microbial species and can provide stability, long retention time of microbes and much less surplus sludge. Third, the coexistence of aerobic and anoxic zones within the biomass film could provide an opportunity for simultaneous nitrification and denitrification to occur. Fourth, the biofilm processes are less sensitive to the toxic condition and other adverse operational conditions, thus making them easy to operate and maintain. Finally, problems caused by poor settling of sludge and sludge bulking would not be encountered during operation [41]. IV. MATERIALS AND METHODS 4.1 Fluidized Bed Biofilm Reactor (Denitrifying Unit) The experimental setup used for this study is shown in Figure 1. Its main part is the 1.22 l reactor made of Plexiglas tube (0.036 m diameter, 1.20 m long), which is fixed to a steel stand. It is filled with uniform bone china fine granules as a biofilm carrier to a settled depth of 0.30 m. At the bottom, a small closed influent tank of 6 l capacity is provided to which pump is fitted which supplies the influent to the reactor. At the top of the reactor an outlet pipe (tube) is joined which collects the effluent from the reactor and discharge again into influent tank. At the inlet of the reactor, a regulator cock is provided to regulate the flow as well as fluidization of media in the reactor. Fine screens are provided at both the ends (bottom and top end) of the reactor to avoid escape of media from the reactor and also to distribute the flow uniformly in the reactor. pH, temperature, alkalinity, COD and NO3 - N concentrations were systematically recorded at the end of each run. 4.2 Biofilm Carrier Media Various materials have been tried by researchers as biofilm carrier media. e.g. sand, glass beads, activated carbon, cement ball [18], plastic, etc. In this study bone china fine granules were used as biofilm carrier media. It is prepared by crushing and sieving waste bone china (crockery) material. The characteristics found after performing particle size distribution of bone china fine granules were – Effective size (D10) 0.129 mm, Coefficient of Uniformity Cu (D60/D10) 3.648, Coefficient of curvature or gradation Cc ((D30)2 /(D60*D10)) 0.019, and Specific gravity 2.26. 4.3 Feed A synthetic medium (synthetic wastewater) was prepared using deionized water in addition to the other chemicals. Potassium nitrate (KNO3) was added as the nitrogen source at different varying concentrations of NO3 - -N in mg l-1 . PO4 3- (as Na2HPO4.12H2O and KH2PO4) both as P source and medium buffering agent. Trace mineral constituents essential to the bacterial growth added per liter were : 0.85 mg FeSO4.7H2O, 0.25 mg Na2MoO4.2H2O, 0.157 mg MnSO4.7H2O and 33 mg NaHCO3. Sodium sulfite and Cobalt chloride were added at concentrations of 20 and 0.55 mg l-1 respectively, to reduce the oxygen concentration to below 0.5 mg l-1 to ensure anoxic conditions in the reactors [42]. The Methanol was used as carbon source. The concentration of NO3 - - N and methanol in the medium was varied at different stages of the study to maintain (methanol/NO3 - -N) ratio. 4.4 Operation of a Fluidized Bed Biofilm Reactor Figure 1 shows schematic diagram of the FBBR which was operated daily for denitrification, nearly for a year. The reactor was inoculated with domestic wastewater and run by feeding synthetic medium for 15 days. After getting proper results, the reactor was operated for 75 days to find out optimum methanol/NO3 - - N ratio. For this, reactor was run for 15 days each for each methanol/NO3 - - N ratio of 2.25, 2.50, 2.75, 3.00 and 3.25. Average NO3 - - N removal efficiency obtained was 67.95%, 78.96%, 84.55%, 89.88% and 86.63% for methanol/NO3 - - N ratios 2.25, 2.50, 2.75, 3.00 and 3.25 respectively. Hence, the ratio of 3.00 was finalized for the present study.
  • 5. Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal www.ijres.org 42 | Page Figure 1. Experimental Setup of Fluidized Bed Biofilm Reactor. For Experimental work, by maintaining constant methanol/NO3 - - N ratio as 3.00, the synthetic wastewater samples were prepared for varying concentration of NO3 - -N of 10.00 mg l-1 , 20.00 mg l-1 , 30.00 mg l-1 , 40.00 mg l-1 , 50.00 mg l-1 , 60.00 mg l-1 , 70.00 mg l-1 , 80.00 mg l-1 , 90.00 mg l-1 and 100.00 mg l-1 . For these each concentrations of NO3 - -N, the reactor was run for 10 days and various characteristics of influent and effluent were measured at the end of each run (i.e. hydraulic retention time (HRT) of 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes). The characteristics measured were temperature, pH, alkalinity, COD and NO3 - -N. 4.5 Analytical Methods Samples were collected from the FBBR at regular intervals. These samples were tested for various characteristics. pH was measured by digital pH Meter. Alkalinity was determined by titration method according to APHA [1]. COD was measured by reflux method according to APHA [1]. NO3 - -N was measured by UV- Spectrophotometer (Schimadzu make, Model – UV 1650). V. RESULTS AND DISCUSSION The experimental denitrification reactor was operated for 10 different concentrations and readings were recorded at HRT of 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, and 30 minutes. The NO3 - -N removal was determined on the basis of the results of analysis of medium entering and leaving the reactor for methanol/ NO3 - -N ratio of 3.00. Average NO3 - -N removal Efficiency was found to be 60.60%, 86.86%, 88.77%, 90.72%, 91.75% and 92.26% for HRT of 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, and 30 minutes respectively. The results are shown graphically in Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6, and Fig. 7. In this study, it was found that, NO3 - -N removal efficiency was in the increasing order for the increasing concentration of NO3 - -N up to 70 mg l-1 , after this trend was declining. NO3 - -N removal efficiency for hydraulic retention time of 30 minutes for NO3 - -N concentration of 10 mg l-1 , 20 mg l-1 , 30 mg l-1 , 40 mg l-1 , 50 mg l-1 , 60 mg l-1 and 70 mg l-1 was 91.52%, 92.17%, 92.10%, 92.45%, 92.72%, 92.64% and 93.71%. And NO3 - -N removal efficiency after 30 minutes for NO3 - -N concentration of 80 mg l-1 , 90 mg l-1 and 100 mg l-1 was 92.19%, 91.60%, 91.51%. Fig. 8 shows graphical representation of NO3 - -N removal % for different HRTs. From the Figure, it was observed that, as the concentration of NO3 - -N increases in the wastewater sample (i.e. from 10.00 mg l-1 to 70.00 mg l-1 ) there was a gradual increase in NO3 - -N removal. But after this there was a slight decrease in NO3 - -N removal rate. This might be due to less concentration of available NO3 - -N present in the wastewater. Fig. 9 shows the graphical representation of NO3 - -N removal % for wastewater containing varying concentrations of NO3 - -N at different HRTs. From the readings and figures, it was observed that most of the NO3 - -N was removed at HRT of 10 minutes. There is a very little difference between NO3 - -N removal % at HRT of 10 and 30 minutes. Thus HRT of 10 minutes can be considered as optimum condition. Inlet Tank Glass Tube (0.036 M Dia, 1.20 M long) Fluidized Media Regulator Cock Pump Inlet Pipe Outlet Pipe Denitrifying Reactor Figure 1 : Experimental Setup of Fluidized Bed Biofilm Reactor Synthetic Wastewater
  • 6. Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal www.ijres.org 43 | Page In the present study, the nitrogen loading rates varied from 0.48 kg N m-3 d-1 to 28.80 kg N m-3 d-1 . For these nitrogen loading rates, denitrification rates observed vary from 0.44 kg N m-3 d-1 to 17.26 kg N m-3 d-1 . But optimum (at maximum NO3 - -N removal efficiency), nitrogen loading rate and denitrification rate observed were 10.08 kg N m-3 d-1 and 8.88 kg N m-3 d-1 respectively. Rezaee et al. [44], in their study to investigate technical feasibility of biological nitrate removal in a packed bed reactor using microbial cellulose as biopolymer carrier, got denitrification rate of 4.7 kg NO3 - -N m-3 d-1 for loading rate of 5.64 kg NO3 - -N m-3 d-1 . The biofilm reactors give high nitrate removal rate from 3.1 - 4.4 kg NO3 - -N m-3 d-3 to 10 – 12 kg NO3 - -N m-3 d-3 [25]. Rabah [42], presented the results of his study in comparison with the other studies in which fluidized bed reactors were reportedly used with methanol as the carbon source (Table 1). Results found by Rabah [42] were found to be in agreement with the results obtained in this research. 54 56 58 60 62 Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10 NO3 --NRemoval(%) Day Fig. 2 : NO3 --N Removal after 5 Minutes (HRT) for Different Concentrations of NO3 --N NO3--N = 10 mg/l NO3--N = 20 mg/l NO3--N = 30 mg/l NO3--N = 40 mg/l NO3--N = 50 mg/l NO3--N = 60 mg/l NO3--N = 70 mg/l NO3--N = 80 mg/l NO3--N = 90 mg/l NO3--N = 100 mg/l 82 84 86 88 Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10 NO3 --NRemoval(%) Day Fig. 3 : NO3 --N Removal after 10 Minutes (HRT) for Different Concentrations of NO3 --N NO3--N = 10 mg/l NO3--N = 20 mg/l NO3--N = 30 mg/l NO3--N = 40 mg/l NO3--N = 50 mg/l NO3--N = 60 mg/l NO3--N = 70 mg/l NO3--N = 80 mg/l NO3--N = 90 mg/l NO3--N = 100 mg/l 86 87 88 89 90 91 92 Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10 NO3 --NRemoval(%) Day Fig. 4 : NO3 --N Removal after 15 Minutes (HRT) for Different Concentrations of NO3 --N NO3--N = 10 mg/l NO3--N = 20 mg/l NO3--N = 30 mg/l NO3--N = 40 mg/l NO3--N = 50 mg/l NO3--N = 60 mg/l NO3--N = 70 mg/l NO3--N = 80 mg/l NO3--N = 90 mg/l NO3--N = 100 mg/l 86 87 88 89 90 91 92 Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10 NO3 --NRemoval(%) Day Fig. 5 : NO3 --N Removal after 20 Minutes (HRT) for Different Concentrations of NO3 --N NO3--N = 10 mg/l NO3--N = 20 mg/l NO3--N = 30 mg/l NO3--N = 40 mg/l NO3--N = 50 mg/l NO3--N = 60 mg/l NO3--N = 70 mg/l NO3--N = 80 mg/l NO3--N = 90 mg/l NO3--N = 100 mg/l
  • 7. Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal www.ijres.org 44 | Page 89 90 91 92 93 94 Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10 NO3 --NRemoval(%) Day Fig. 6 : NO3 --N Removal after 25 Minutes (HRT) for Different Concentrations of NO3 --N NO3--N = 10 mg/l NO3--N = 20 mg/l NO3--N = 30 mg/l NO3--N = 40 mg/l NO3--N = 50 mg/l NO3--N = 60 mg/l NO3--N = 70 mg/l NO3--N = 80 mg/l NO3--N = 90 mg/l NO3--N = 100 mg/l 89 90 91 92 93 94 Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7 Day 8 Day 9 Day 10 NO3 --NRemoval(%) Day Fig. 7 : NO3 --N Removal after 30 Minutes (HRT) for Different Concentrations of NO3 --N NO3--N = 10 mg/l NO3--N = 20 mg/l NO3--N = 30 mg/l NO3--N = 40 mg/l NO3--N = 50 mg/l NO3--N = 60 mg/l NO3--N = 70 mg/l NO3--N = 80 mg/l NO3--N = 90 mg/l NO3--N = 100 mg/l 58 63 68 73 78 83 88 93 10 20 30 40 50 60 70 80 90 100 NO3 --NAxisRemoval(%) NO3 -- N Concentration mg l-1 Fig. 8 : NO3 -- N Removal (%) for Different HRTs for Different Concentrations of NO3 -- N HRT = 05 Minutes HRT = 10 Minutes HRT = 15 Minutes HRT = 20 Minutes HRT = 25 Minutes HRT = 30 Minutes 58 63 68 73 78 83 88 93 5 10 15 20 25 30 NO3 --NRemoval(%) Hydraulic Retention Time in Minutes Fig. 9 : NO3 --N Removal for Different Concentrations of NO3 --N at Different HRTs Nitrate N = 10 mg/l Nitrate N = 20 mg/l Nitrate N = 30 mg/l Nitrate N = 40 mg/l Nitrate N = 50 mg/l Nitrate N = 60 mg/l Nitrate N = 70 mg/l Nitrate N = 80 mg/l Nitrate N = 90 mg/l Nitrate N = 100 mg/l
  • 8. Performance of Fluidized Bed Biofilm Reactor For Nitrate Removal www.ijres.org 45 | Page Table 1: Comparison of some studies on denitrification using fluidized bed reactors Form of Nitrogen Temperature (0 C) Concentration of Nitrogen (mg l-1 ) Denitrification Rate (kg N m-3 d-1 ) References NO3 – N 18-23 5 – 100 5.4 – 20.70 Jeris and Owens (1975). NO3 – N - 6.6 – 30 0.69 – 3.28 Hermanwicz and Cheng (1990). NO3 – N 30 15 – 300 3.23 – 18.70 Hirata and Meutia (1996). NO3 – N 20 20 3.5 MacDonald (1990). NO3 – N - 676 – 1500 11.8 – 17.7 Chen et al (1996). NO3 – N 23 1000 12 Rabah Fahid K. J., et al, (2004). NO3 – N 24.5 – 40.5 10 – 100 0.44 – 17.26 (Optimum 8.88) This Study Courtesy: Rabah [42]. Heterotrophic denitrification causes a release of hydroxyl ions and raises alkalinity. Each mg of nitrate- N reduced to N2 causes an alkalinity increase of 3.57 mg CaCO3 [45]. In this study, average g of Alkali produced per g of NO3 - -N removed was found to be 3.60 which is in agreement with the value found in literature. As alkalinity is produced, there is a rise in pH. pH of the influent was in the range of 6.56 – 7.15 and that of effluent observed was in the range of 6.76 – 8.06. The denitrification intensity depends on carbon availability. The carbon to nitrogen ratio in the biological reactor influent should be high enough to denitrify all nitrates arisen in the nitrification process. Komorowska-Kaufman [24], mentioned in his paper, many researchers’ work revealed the g ∆COD/g ∆N ratio as 3.5 – 4.5. In the present study, based on all the results, average g of COD consumed per g of NO3 - -N removed is found to be 3.70. This is in confirmation with the results obtained by many researchers. VI. CONCLUSION The results of the investigation, demonstrated that the trend of the removal of NO3 - -N is quite high up to hydraulic retention time of 10 minutes. An average removal rate at this HRT observed was 88.13%. Also on the initial NO3 - -N concentration basis, it was observed that for initial concentrations upto 70 mg l-1 , the NO3 - -N removal rate was in increasing order but for higher concentrations, the trend was slightly declining. The efficiency can be improved by using special culture of denitrifying microorganisms in the FBBR. The result of this study demonstrated conclusively that FBBR with bone china fine granules as a biofilm carrier media can be used with great advantages for denitrification. This study provides the justification for the recommendation of FBBR for denitrification by many researchers. VII. ACKNOWLEDGEMENT We are grateful to Principal, Government College of Engineering, Amravati and Incharges of Environmental Engineering Laboratory at Government College of Engineering, Amravati Prof. Mokadam A. M., Prof. Gulhane M. L. and Prof. Rai R. K. for giving permission to carry out laboratory work in their Institute and their guidance and timely help. We are also thankful to Prof. D. N. Shingade, Principal, Government Polytechnic, Amravati, for giving permission to carry out the present study. S. P. Burghate received M. E. (Environmental Engineering) from Government College of Engineering, Amravati, Maharashtra, India in 1992. He is Lecturer in the Department of Civil Engineering, at Government Polytechnic, Amravati, Maharashtra, India. His research interests include treatment of water and wastewater, solid waste management. He has published 5 papers in National and International journals. He has also presented 6 research articles in national and international conferences. He is a Life Member of professional bodies like, IE (India), ISTE (India), and IWWA. Dr. N. W. Ingole is a Professor and Head in the Department of Civil Engineering, Prof. Ram Meghe Institute of Technology and Research, Badnera, Amravati, Maharashtra, India. He has more than 24 years of experience in teaching and research. His current area of research includes treatment of water and wastewater, solid waste management, Quality Engineering, Neural Networks, Optimization and Simulation. He has published more than 63 papers in refereed National and International journals of repute. He has also presented more than 10 research articles in national and international conferences. He has written a book titled “Environmental Chemistry and Pollution Control”. He is life member of National and International Professional Societies, Fellow of Institution of Engineers (India). He is recipient of many National and International awards. He has also got “Promising Engineering Teacher in Engineering Colleges Award”. He is currently dealing with few projects sponsored by government of India.
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