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INTRODUCTION
1.1 GENERAL
1
1.2 SOURCES OF POLLUTION
The Slaughterhouse industry is one of the largest and most polluting
industries in the world. In Slaughterhouse the processing and subsequent
bleaching is done using large quantity of water and they are discharged as
effluent. The most significant sources of pollution are waste preparation,
pulping, pulp washing, screening, washing, bleaching and machine and coating
operations. Among the processes, pulping generates high strength waste water
especially by chemical pulping. This wastewater contains meat debris and
soluble meat materials.
Industrial effluent from Slaughterhouse contains several toxic and non-
biodegradable organic materials, which include sulfur compounds, pulping
chemicals, organic acids, chlorinated lignins, resin acids, phenolics, unsaturated
fatty acids and terpenes. Slaughterhouse are voracious water users. Their
consumption of fresh water can seriously harm habitat near , reduce water
levels necessary for fish, and alter water temperature, a critical environmental
factor for fish. They also increase the amount of toxic substances in the water
2
causing death to the zoo plankton and fish, as well as profoundly affecting the
terrestrial ecosystem (Pokhrel and Viraraghavan, 2004).
3
Wastewater(m /adt SS (kg/adt COD (kg/adt
Process meat or slaughter)
Kraft unbleached 40-60 10-20 40-60
Kraft bleached 60-90 10-40 100-140
CTMP unbleached 10-15 20-50 70-120
CTMP bleached 10-15 20-50 100-180
Paper making 10-50 - -
Agro based small
200-250 50-100 1000-1100
paper
3
from individual pulping and papermaking process. Table 1.2 shows the
performance data of selected processes and mills. Table 1.3 shows the general
characteristics of wastewater produced at various process stages. Table 1.4
shows the characteristics of raw pulp bleaching effluent from extraction stage
(exclusive of washing) which was collected from a bamboo based local pulp
and paper industry.
Parameter Values
pH 9.8
Color Dark brown
Suspended solids ( mg/L) 85
Total dissolved solids (mg/L) 2380
COD (mg/L) 1410
4
Table 1.5 Raw waste water characteristics of a Indian meat
Parameter Values
pH 10
BOD5 (mg/L) 400
Total COD (mg/L) 964
Soluble COD (mg/L) 950
Total solids (mg/L) 1396
Dissolved solids (mg/L) 1132
Suspended solids (mg/L) 264
Color (PtCo) (mg/L) 4236
Parameter Values
pH 6.86 – 7.12
BOD (mg/L) 615 - 670
COD (mg/L) 2000 -2100
Total solids (mg/L) 2100
Suspended solids (mg/L) 40
Dissolved solids (mg/L) 1760
COD/BOD 2.99
Color (PtCo) 1750
5
Table 1.7 Characteristics of agro based black liquor
Raw materials
Parameters Bagasse, Wheat straw Rice straw
Wheat
straw
0
pH at 25 C 9.7 10.2 8.8
BOD (mg/L) 15500 13800 16500
COD (mg/L) 48700 45600 40000
Lignin (mg/L) 16000 13200 14400
Total dissolved solids 44000 42000 38000
(mg/L)
COD/BOD 3.36 3.3 2.42
Biodegradability (%) 48 55 38
From the above tables, it was observed that the pH of the wastewater
ranges from 6.86 to 10.2. The BOD of the untreated wastewater ranges between
400 to 16500 mg/L. The COD ranges between 950 to 40000 mg/L and
suspended solids ranges between 56 to 264 mg/L. The untreated wastewater
cannot be discharged to the environment with the above characteristics.
Therefore the wastewater has to be treated to bring down the value to the
permissible limits according to MINAS disposal limits.
6
Table 1.8 MINAS disposal limits
7
1.7 NEED FOR THE STUDY
Generation of wastewaters in industrial processes is sometimes
unavoidable and in most cases a process to reduce the organic load and other
contaminants must be employed before water discharge. The figure 1.2 shows
the layout of the treatment plant. The effluent is collected from the collection
tank. Then it is fed into the primary clarifier where alum, lime to precipitate the
such as CO2 and H2O under moderate conditions. The AOPs are characterized
by the production of ˙OH radicals which are an extraordinary reactive species
and capable of mineralizing organic pollutants. The solar Photo-Fenton process
has proved to be rather effective in degradation and mineralization of organic
pollutants.
8
agitator
settling agent
effluent
equalization
primary
clarifier
tank
collection tank
centrifuge
drying bed
9
1.8 OBJECTIVES
To evaluate the effectiveness of Photo-Fenton process for the treatment of
pulp and paper mill wastewater.
Collection and characterization of the pulp and paper mill wastewater.
To fabricate the lab scale solar Photo-Fenton reactor.
2+
To study the effect of operating conditions namely pH, Fe , H2O2, liquid
depth, biodegradability and irradiation time.
After optimizing all the parameters, kinetics has to be arrived and to design
the pilot plant reactor and the treatment costs will be evaluated.
CHAPTER 2
REVIEW OF LITERATURE
2.1 GENERAL
The increasing industrialization and its effluent discharges have
accentuated the environmental problems to a large extent. Besides many other
industries, the pulp and paper industries are also responsible for creating major
water pollution. Various treatment processes are used for treating the waste
water from pulp and paper industry.
2.3.1 Screening
The wastewater is passed through the multiple screens to remove the
coarse materials present in the raw wastewater from the pulp and paper mill.
2.3.3 Sedimentation
The removal of suspended and colloidal materials from wastewater by
gravity separation is one of the most widely used unit operations in wastewater
treatment. In most cases, the primary purpose is to produce a clarified effluent,
but it is also necessary to produce sludge with a solids concentration that can be
handled and treated easily.
Suspended matters present in the pulp and paper wastewater are
comprised primarily of bark particles, fiber, fiber debris, and filler and coating
materials. (Thompson et al. (2001) stated that sedimentation was the preferred
option within the paper mills in the U.K, and contributed to more than 80%
removal of the suspended solids on an average. The maximum percentage
removal of TSS is 98%.
as (Al2 (SO4)3). Chitosan was far more effective in removing these pollutants
than other coagulants. It eliminated up to 90 % of the color and 70 % of the
total organic carbon. The maximum COD removal is 83% and maximum color
removal is 92% (Pokhrel and Viraraghavan, 2004).
2.3.6.1 Photocatalysis
Photo catalysis is carried out in an irradiated reactor that contains a
The polluting power of dairy serum is very high and, the previous treatment with
natural and conventional treatment plants does not fulfill its function, because of the
wealth of organic materials carried in lactic sera. The proteins and the lactose become
contaminants when the liquid is discharged into the environment without any type of
treatment, because the load of organic matter that it contains allows the reproduction
of microorganisms. The dairy wastewaters can be partly reused or treated. Biological
processes are usually preferred to treat dairy wastewaters like treatment in ponds,
activated sludge plants and anaerobic treatment.
The most common purification methods used for the treatment of the discharge liquids
produced by the meat and dairy industries, the anaerobic treatments, are insufficient
and have important consequences that have been little studied with regard to microbial
flora dragging. The problem is when these effluents, poorly cleared and with large
biological contributions, are discharged into public waterways, due to unawareness of
their impact on health. The anaerobic digestion process is an imperative tool for the
production of clean energy sources, such as hydrogen and methane. Liquids produced
by the meat and dairy industries can be processed with anaerobic digestion to produce
biogas that can be used to generate heat or electricity. The biogas can be used in a
cogeneration system or used for bio methane production which in turn can be sent to
national natural gas network or used as a bio combustible fuel in the automotive
sector. There are several studies on the optimization of this process to obtain biogas
from slaughterhouse waste to solve this problem. In this work, the influence of the
addition of animal dairy serum on the anaerobic codigestion of solid and liquid waste
from the municipal slaughterhouse of Badajoz has been studied. From the results of
the codigestion of the effluent of solids (viscera and offal), purines, blood and cleaning
d with an HRT of 18 days and produce methane up to 0.33 m3/kg VSadded (Table 3).
On the other hand, under similar conditions, digesters inoculated with mesophilic
and thermophilic granular sludge failed apparently because of inhibition by ammonia
and/or LCFAs (Salminen and Rintala, 1999). Co-digestion of manure and industrial
organic wastes, including slaughterhouse waste, takes place in Denmark in a number
of anaerobic digestion plants (Danish Institute of Agricultural and Fisheries
Economics, 1999). Manure and slaughterhouse waste, including blood, fat, stomach,
and visceral contents, and residues from a rendering plant, are also being treated in a
plant in Sweden (Ling, 1997) (Table 3). Rosenwinkel and Meyer (1999) showed a
successful treatment of slaughterhouse waste, hog, and cow stomach contents with
sewage sludge in a pilot-scale, mesophilic digester at a loading of 2.9 kg TS/m3 d and
an HRT of 17 days with a methane production of 0.23m3=kg TSadded. In another
study, methane production in a sewage sludge digester treating flotation tailings was
possible at a loading of 1.5 kg TS/m3 d and an HRT of 15 days with a methane
production of 0.32m3=kg TSadded (Table 3). Brinkman (1999) described a stable,
thermophilic treatment of kitchen waste slurries and flotation sludges from
slaughterhouse wastes in alaboratory-scale digester at a loading of less than 3.5 kg
COD/m3 d with an HRT of 32days, but shock loads of 5–7.5 kg COD/m3 d caused an
accumulation of LCFAs and VFAs. 5.4. Slaughterhouse wastewaters Anaerobic
treatment of slaughterhouse wastewater is far more common than the treatment ofsolid
slaughterhouse waste. In 1968 in Leeds, the UK, an anaerobicplant was built to treat
slaughterhouse wastewater
2.4 STUDIES ON OTHER TREATMENT PROCESSES
The other treatment processes are adsorption, aerated lagoons, anaerobic
treatment and membrane filtration.
2.4.1 Adsorption
Abu et al., (2008) conducted a study using Granular Activated Carbon –
Sequencing Batch Biofilm Reactor (GAC-SBBR) of 3.0L working volume,
operated in an aerobic condition and packed with 200g/l of 2-3 mm granular
activated carbon (coconut shells) as a medium for the biofilm growth. The
results showed that the biofilm attached onto granular activated carbon (GAC)
can remove the recalcitrant organics in the wastewater, within the range of 10 –
100% AOX removal depending on the selected HRTs.
Netnapid et al. (2004) conducted batch experiments for the removal of
color, COD and lignin in Slaughterhouse waste water of using white wood ash
and black wood ash that generated from boilers unit in the Slaughterhouse. It
was found that the removal of color is 89 – 93% COD is 66 – 70% and lignin is
78 – 82 % when white wood ash is used
Mominur and Kazi (2010) conducted physicochemical treatment
processes that remove suspended solids, colors, BOD and COD by screening,
coagulation, flocculation, sedimentation, floatation, adsorption etc. It was found
that the TSS removal was 91.2%, BOD 5 removal was 89%, COD removal was
84%.Initially, the effluent was turbid/white, but after treatment it becomes
colorless.
3.1 GENERAL
The Slaughterhouse is one of the most important in the world, but it
discharges a variety of gaseous, liquid and solid wastes into the environment.
The pulp and paper mill wastewater was treated by Ferric coagulation process.
The parameters such as pH, reagent concentration and time were optimized to
achieve high COD, color and toxicity reduction.
Parameters Reference
+
pH 4500-H , APHA 2005
TSS (mg/L) 2540 B, APHA, 2005
COD (mg/L) 5220 B, APHA, 2005
BOD (mg/L) 5210 B, APHA, 2005
Treatment of Slaughterhouse wastewater by ferric coagulation process
Operating parameters
pH - 2 to 4
Kinetic study
Cost analysis
3.5.1 Effect of pH
The degradation of the waste material under the sunlight and the COD
removal in different reactions was found to be dependent on pH of the solution
(Bidhan et al., 2009). Therefore pH is an important parameter and it affects the
efficiency of the Fenton’s treatment process. In order to study the effect of pH,
it was varied in the range of 2 to 7 and the reaction was carried out for 1 hour
2+
with the dosage of Fe - 1g/L and H2O2 - 15g/L. The sample was taken for
every five minutes and it was quenched by adding sodium sulfite. The treated
wastewater sample was then filtered to separate the catalyst. The supernatant
was taken to analyze the color and COD.
TiO2 was varied in the range of 0 to 1.5 g/L with the optimum pH and the
solar/ TiO2/H2O2.It was found that by drawing a graph between irradiation time
and color removal. The kinetic degradation was studied for solar, Dark reaction,
solar/ TiO2/H2O2.
The pilot plant reactor was designed to treat the pulp and Slaughterhouse
wastewater based on the flow rate. The cost of chemicals was calculated based
on the amount of chemicals needed for treating the wastewater.
CHAPTER 4
4.1 GENERAL
Parameters Values
pH 7.11 -7.25
TS (mg/L) 9677.5
COD (mg/L) 2133
BOD (mg/L) 60
Color Brown
.
4.3 EFFECT OF OPERATING PARAMETERS
4.3.1 Effect of pH
The effect of pH was studied by varying the pH from 2 to 7 with the
dosage of TiO2 = 1g/L and H2O2 = 15 g/L. From the figure 4.1, it is clear that
at pH4, 100% color was removed within 10 minutes of irradiation time. The
decolorization decreases as the pH increases from 5 to 7. The percentage
removal of color and COD are given in table 4.2 and table 4.3 respectively.
According to Hsueh et al., 2005, the decrease of decolorization with the
3+
increase in pH is due to the fact that the hydrolysis of Fe in the solution
˙
reduces the rate of OH production.
% color removal
Time(min)
pH2 pH3 pH4 pH5 pH6 pH7
5 82.2 97.5 98 91.5 91.2 90.2
10 95.5 98 99.2 91.7 91.5 91.8
15 98.7 99.5 99.9 92.2 93 92.3
20 98.9 99.9 99.9 92.8 93.5 92.5
25 99 99.9 99.9 93.5 95 93.8
30 98.5 99.9 100 95.8 94.5 94
complexes and also due to the decomposition of H 2O2. Hence the maximum
removal of color and COD removal was obtained at pH 4.This is due to the
+
formation of dominating species of Fe (OH) .This form of iron species could
be generated at pH 2-4 and its activity is higher than the non-complex form of
105
100
%color removal
95
pH3
90 pH2
pH4
pH5
85
pH6
pH7
80
5 10 15 20 25 30
Time (min)
95
90
85
% COD
removal 80
75
70
65
60
55
50
pH2 pH3 pH4 pH5 pH6 pH7
oxonium ions made H2O2 electrophilic to enhance its stability and presumably
to reduce substantially the reactivity with ferrous ion (Lee et al., 1999). Sheik et
al., 2008 studied the optimum pH’s for the degradation of p-aminophenol, p-
nitroaniline and acetanilide are 3, 3.5 and 2.5 respectively.
4.3.2 Effect of TiO2 concentration
investigated by varying the dosage of TiO2 from 0 to 1.5 g/L. From the figure
2+
4.3 and figure 4.4, it was observed that as the concentration of Fe increased
from 0 to 1.5, 99% of color was removed within 10 minutes. Also degradation
the TiO2 dosage was 1.0 g/L and it was taken as the optimum dosage. This is
because the catalyst ferrous sulphate accelerates the decomposition of H 2O2.
The results are shown in table 4.4 and table 4.5 .
% color removal
Time
2+
(min) Fe Conc. 0 g/L 0.5 g/L 1 g/L 1.5 g/L
5 67.6 91 95.1 94
10 85.5 95 99.1 96.5
15 90.1 98 99.5 99.5
20 94.5 99.6 99.6 99.9
25 95 99.9 100 100
30 96 100 100 100
radicals. Bidhan et al., (2009) found the optimum dosage of FeSO 4 as 280
mg/L. Nogueira et al., (2008) conducted a study on the solar driven ferric
coagulant process for treating water containing phenol as a contaminant
evaluated by means of pilot-scale experiments with a parabolic trough solar
reactor (PTR). About 90% of DOC was removed within 3 hours of irradiation
or less under the optimum Fe (II) in the range of 0.04 – 1.0 mmolL-1.
105
100
95
% color 90
removal 0 g/L
85
0.5 g/L
80
1.0 g/L
75
70 1.5 g/L
65
60
5 10 15 20 25 30
Time (min)
95
% COD 90
removal
85
80
75
70
0 0.5 1 1.5
The effect of H2O2 was investigated with the optimized value of TiO 2 =
1 g/L and pH= 4 and by varying the dosage of H 2O2 from 0 to 25 g/L. The
˙
H2O2 + OH˙ HO2 + H2O ……. (4.1)
˙
HO2 + OH H2 O + O 2 ……. (4.2)
˙ ˙
OH + OH H2 O2 ……. (4.3)
Table 4.6 Effect of H2O2 on color removal
% color removal
Time
H2O2 5 g/L 10 g/L 15 g/L 20 g/L 25 g/L
(min)
conc.
5 95.6 97.9 96 96 96.5
10 99 99.5 99 99 99
15 99.5 99.9 99.5 99.5 99.5
20 99.9 99.9 99.7 99.7 99.7
25 99.9 99.9 99.8 99.8 99.8
30 99.9 99.9 99.9 99.9 99.9
100
99
% color
removal
98
5 g/L
97 10 g/L
15 g/L
20 g/L
96
25 g/L
95
5 10 15 20 25 30
Time(min)
H2O2 concentration
COD (mg/L) % COD removal
(g/L)
5 149 93
10 127 94
15 100 95.4
20 170 92
25 297 86
Dixit et al., (2010) reported that the maximum degradation of 74.6% and
79.8% of phenol and chlorophenol respectively within 90 minutes of radiation
time with H2O2 concentration varying from 200 – 550 ml/L. Bidhan et al.,
(2009) reported that the optimum dose of H2O2 for the degradation of pyridine
was 87 mM with the COD reduction of 74%.The rate of degradation decreases
as H2O2 increases after optimum condition, this is because that more H 2O2
molecules are available for TiO2 ions to react, which increases the number of
.
OH radicals. Therefore, the rate of reaction also increases the rates of the
.
reaction become fast and OH radicals are consumed rapidly due to more
availability of H2O2 molecules (Anil Kumar et al., 2008).
100
95
% COD
removal
90
85
80
75
5 10 15 20 25 Time(min)
ferrous sulfate (TiO2 = 1g/L) and hydrogen peroxide (H2O2 = 5 g/L) were
added and stirred well. The ferric coagulation reactions were carried out under
strong solar radiation from 12.00 pm to 1.00 pm. The samples were taken for
every five minutes to analyze COD and color. The percent removal of COD is
given in table 4.8.
From the figure 4.7, it was observed that the color removal was nearly
the same in all the heights with the slight differences. Maximum color removal
was achieved within 10 minutes of irradiation time. But in the case of COD
removal, the depth plays an important role. As the depth increases, the
degradation of COD decreases. This is because, for smaller depths, light can
penetrate well. As the depth increases, the light cannot penetrate deep into the
reactor for photolysis. Janhavi et al., 2008, reported that shallow solar pond
having depth of 2 cm gives the best results.
100
95
90
% COD
removal 85
80
75
70
65
60
2.3 4.6 7.2 9.7 12.2
Depth in cm
Ahmadi et al., 2008 reported that the short oxidation time along with
smaller initial peroxide concentration provide the highest biodegradability
increase. Enhancement in biodegradability makes way for coupling ferric
coagulation and biological treatment processes thereby reducing the cost.
0.9
0.8
0.7
0.6
BOD/CO
D 0.5
0.4
0.3
0.2
0.1
0
0 10 20 30 40 50 60
Time (min)
solar/ TiO2/H2O2.It was found that by drawing a graph between irradiation time
and color removal, first order reaction was found to have maximum value of
2
R .The kinetic degradation was studied for solar, Dark reaction, solar/
TiO2/H2O2. For solar reaction alone, there was no change in color and COD
removal. The results are shown in table 4.10. For dark Fenton reaction, color
removal was about 40% and the COD removal was about 30% and the reaction
-1
kinetic constant was 0.008 min . For solar/ TiO2, the kinetic constant was 0.05
-1 -1
min and solar/H2O2 generates a k value of 0.011min .For Ferric coagulation
-1
process has rate constant value of 0.21 min . Comparing all the
reactions, it was clear from the table; Ferric coagulation processes are three
Table 4.10 First order reaction rate constants for color removal
-1 2
Solar photo-Fenton process by k (min ) R
Dark reaction 0.008 0.97
The pilot plant reactor was designed to treat the Slaughterhouse waste
3
water with the flow rate of 1500 m /d. It was a rectangular tank of size 6.84 m
2
x 4.56 m x 2 m with the surface area of 31.94 m and storage capacity of tank
3
was 62.5 m . The figure 4.9 shows the proposed treatment layout for the
slaughterhouse wastewater. The wastewater from the collection tank was
subjected to sedimentation tank. Then the pH was adjusted to acidic by adding
H2SO4 in the pH dosing tank. Then the wastewater was added with ferrous
sulfate and hydrogen peroxide and stirred well. Again the pH was raised by
adding NaOH to make the ferric hydroxide precipitate to settle at the bottom.
Then the supernatant was passed into the sequential batch reactor where
biological treatment takes place. The treated wastewater can be used for
irrigation purpose. The cost of chemicals required for treating the wastewater
3
was Rs 455 per m .
agitator
settling agent
effluent
primary pH dosing pH dosing
clarifier tank solar photo-Fenton tank TiO2 seperator
reactor
collection tank
clarifier
CONCLUSION
5.1 GENERAL
The literature review showed that an internal process change is one of the
options to be adopted by the Slaughterhouse waste water to reduce the
pollution.
5.2 CONCLUSION
the process is 4.With the ferrous ion dosage of 1 g/L, concentration of H 2O2 as
5 g/L, about 94% of COD was removed within one hour of reaction time and
nearly 100 percent color removal was achieved in a reaction time of 10
minutes. The effect of liquid depth influences the degradation of organic
compound. With the increase in liquid depth, the degradation rate decreases.
The degradation rate of solar/TiO 2/H2O2 process is three times faster than
solar/TiO2 process. For untreated samples, the BOD/COD ratio was 1.089,
while ferric coagulant process enhanced the biodegradability value to 1.089.
Thus coupling of ferric coagulant process with the biological treatment is an
effective treatment method thereby reducing the cost of the treatment.
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standards for the meat and poultry products industry. Office of Water (4303T), Unite
States Environmental Protection Agency (USEPA), EPA-821-B-01007, 2002.
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2000.
4. Banks, C.J. Anaerobic digestion of solid and high nitrogen content fractions of
slaughterhouse wastes. In Environmentally Responsible Food Processing; Niranjan,K.,
Okos, M.R., Rankowitz, M., Eds.;Vol. AIChE Symposium Series. American Institute
of Chemical Engineers: New York, 1994;103–109.
6. Denmead, C.F. Methane production from meat industry wastes and other potential
methods for their utilization, Publication no. 602; Meat Industry Research Institute;
Hamilton, New Zealand, 1977.
9. Brolls, E.K.; Broughton, M. The treatment of effluents arising from the animal by-
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203.
10. Grady, C.P.L.; Lim, H.C. Biological Wastewater Treatment: Theory and
Applications; Marcel Dekker Inc: New York, 1980.
11. AEA Technology. Environmental Technology Best Practice Programme: Reducing
Water and Effluent Costs in Red Meat Abattoirs, Report no. GG234; AEA Technology:
Harwell, UK, 2000.
12. Johnson, A.S. Meat. In Industrial Wastewater Control; Gurnham, C.F., Ed.;
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13. World Bank. Meat processing and rendering. In Pollution Prevention and
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Nostrand Reinhold: New York,
1998; 427–432.