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CHAPTER 1

INTRODUCTION

1.1 GENERAL

Anaerobic – aerobic systems have been remarkably employed in


industrial and municipal wastewater treatment for many years. While previously
most treatment of wastewaters have been carried out inconventional anaerobic–
aerobic treatment plants, in recent years, high rate anaerobic–aerobic bioreactors
have been increasingly employed for wastewaters with high chemical oxygen
demand (COD).This paper provides a review of the various types of high rate
anaerobic–aerobic water treatment techniquescurrently available including high
rate bioreactors and integrated anaerobic–aerobic bioreactors.
The integrated bioreactors are classified into four types, which are (i) integrated
bioreactors with physicalseparation of anaerobic–aerobic zone, (ii) integrated
bioreactors without physical separation of
anaerobic–aerobic zone, (iii) anaerobic–aerobic Sequencing Batch Reactors
(SBR), and (iv) combined
anaerobic–aerobic culture system. The integration of aerobic and anaerobic
degradation pathways in a single bioreactor is capable of enhancing the overall
degradation efficiency. The merits of different integrated
anaerobic–aerobic bioreactors are highlighted and comparison made to identify
possible future areas of research to fully utilize these methods of wastewater
treatment.

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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

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causing death to the zoo plankton and fish, as well as profoundly affecting the
terrestrial ecosystem (Pokhrel and Viraraghavan, 2004).

Table 1.1 Typical wastewater generations and pollution load from


Slaughterhouse waste water

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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

Table 1.2 Typical pollution loads per ton of production (kg/ton).

Process SS BOD COD Color Reference


Wood yard 3.75 1 - 2 Springer(2000)
Pulping 13.5 5 - 1.5 Springer(2000)
Bleaching 6 15.5 - 40 Springer(2000)
Paper making 30.8 10.8 - 1.5 Springer(2000)
Large mill 31.2 13 82.4 - Srinivastava
et.al (1990)
Small mill 140.3 152.26 639.4 - Srinivastava
et.al (1990)

1.4 WASTEWATER CHARACTERISTICS


The characteristics of the waste water generated from various processes
of the pulp and paper industry depend upon the type of the process, type of the
wood materials, process technology applied, management practices, internal
circulation of the effluent for recovery, and the amount of water to be used in
the particular process. The general characteristics of wastewater produced at
various stages are given below. Table 1.1 shows the wastewater pollution load

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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.

Table 1.3 Typical characteristics of waste water at different processes

Process pH SS (mg/L) BOD5 COD (mg/L)


(mg/L)
TMP - 383 2800 7210
CTMP - 500 3000-4000 6000-9000
Kraft bleaching 10.1 37-74 128-184 1124-1738
Sulfite condensate 2.5 - 2000-4000 4000-8000
Paper mill - 800 1600 5020

Table 1.4 Characteristics of raw pulp bleaching effluent

Parameter Values
pH 9.8
Color Dark brown
Suspended solids ( mg/L) 85
Total dissolved solids (mg/L) 2380
COD (mg/L) 1410

Table 1.5 shows the characteristics of Slaughterhouse wastewater from a


Indian meat manufacturer obtained from the equalization tank.

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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

Table 1.6 shows the characteristics of Slaughterhouse effluent.


Table 1.7 shows the characteristics of agro based black liquor.

Table 1.6 Characteristics of Slaughterhouse

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

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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.

1.5 MINAS DISPOSAL LIMITS (Minimum National Standards)


Table 1.8 shows the MINAS disposal limits for the large and small pulp
and paper mill.

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Table 1.8 MINAS disposal limits

Large meat Parameters Concentration


pH 7.0 – 8.5
o
BOD (5 at 20 C ) (mg/L) 30
COD (mg/L) 350
Suspended solids (mg/L) 50
Small meat
Discharge into pH 5.5 – 9.0
inland surface
water Suspended solids (mg/L) 100
BOD (mg/L) 30
Disposal on land pH 5.5 – 9.0
Suspended solids (mg/L) 100
BOD (mg/L) 100

1.6 EFFECTS OF THE SLAUGHTERHOUSE WASTEWATER ON THE


ENVIRONMENT
The pollutants discharged from the Slaughterhouse industry affect all
aspects of the environment such as water, air and land. Various authors reported
the appearance of toxic effects on various species due to exposure of
Slaughterhouse effluents. The toxic effects on various fish species are
respiratory stress, mixed function oxygenase activity, toxicity and mutagenicity,
liver damage, or genotoxic effects, and lethal effects (Owens et al., 1994).
Discharging untreated wastewater causes slime growth, thermal impacts, scum
formation, color problems and loss of aesthetic beauty in the environment.
They also increase the toxic substances in the water. The untreated wastewater
affects health and causes diarrhea, vomiting, headaches, nausea, and eye
irritation on children and workers.

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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

sulphur compounds as CaSO4.Then it enters the equalization tank and before it


enters into the biological treatment, it is supplied with the nutrients. In the
activated sludge process, the bacteria employed are Pseudomonas Aerobacter
and Bacillus. Then it enters the secondary clarifier and the treated effluent is
taken out and the sludge is passed into drying beds.
To remove part of the organic load, biological processes are usually
used, because they are more economical than chemical processes. In some
cases, due to high organic load, toxicity or presence of biorecalcitrant
compounds, biological processes cannot be used, since chemical oxygen
demand (COD) removal cannot be achieved by biological process. Biological
processes do not effectively decolorize the wastewater. Most of the compounds
are refractory compounds-toxic to organisms used for treatment. Detention time
is more and supply of nutrient is necessary. Biodegradation is less.
To increase the efficiency of the process, there is a need for the advanced
treatment. The solar Photo-Fenton process is one of the techniques which are
called “Advanced Oxidation Processes (AOP’s)”.These processes can
completely degrade the organic pollutants into harmless inorganic substances

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.

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agitator
settling agent

effluent
equalization
primary
clarifier
tank

collection tank
centrifuge

sludge nutrient tank


pit aerator
cogeneration
boiler

secondary nutrient tank


treated
clarifier Bio reactor aerator
land use effluent

drying bed

Figure 1.2 Existing conventional treatment layout of Slaughterhouse wastewater

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1.8 OBJECTIVES
ƒ To evaluate the effectiveness of Photo-Fenton process for the treatment of
pulp and paper mill wastewater.
ƒ Collection and characterization of the pulp and paper mill wastewater.
ƒ To fabricate the lab scale solar Photo-Fenton reactor.
2+
ƒ To study the effect of operating conditions namely pH, Fe , H2O2, liquid
depth, biodegradability and irradiation time.
ƒ 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.

2.2 CONVENTIONAL TREATMENT OF PULP AND PAPER


WASTE WATER
Pollution from the pulp and paper industry can be minimized by various internal process
changes and management measures such as the Best Available Technology (BAT).Plant process
modifications and cleaner technologies have the potential to reduce the pollution load in effluents.
However, this approach cannot eliminate waste generation. Assessment of the water quality of the
receiving ecosystems and periodic ecological risk assessments are required to validate the
effectiveness of various treatment methods. Process technologies that are currently applied can be
broadly classified as the physico-chemical and biological treatment methods. These technologies are
discussed in the following sections. The unit processes employed by the pulp and paper industry
during preliminary, primary, secondary, and tertiary stages of effluent treatment are shown in the flow
sheet.

Preliminary Primary Secondary


Final
Influent Screening Sedimentation Activated
effluent
skimming tank sludge

Figure 2.1 Layout of treatment processes


2.3 LEVELS OF TREATMENT
The unit process or operations employed in wastewater treatment
include screening, grit removal, sedimentation, activated sludge, aeration etc.

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.

2.3.2 Skimming tank


The wastewater is then passed into the oil skimming tank.

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%.

2.3.4 Chemical Coagulation and Precipitation


This method relies on the addition of metal salts to cause agglomeration
of small particles into larger flocs that can be easily removed by settling. The
effectiveness of this process depends upon the nature of the coagulating agent,
coagulant dosage, pH, ionic strength, and the nature and concentration of
compounds present in wastewaters. All of the most toxic compounds are
3+
removed through the coagulation using chloride and sulfate salts of Fe and
3+
Al . Dissolved organics are also removed by physical adsorption to flocs. The
generation of chemical sludge and the need for subsequent treatment of the
sludge to eliminate the adsorbed toxic pollutants prior to disposal (Sumathi and
Yung).
S.S Wong et al. (2005) studied the flocculation performances of nine
cationic and anionic polyacrylamides and it was reported that 95% of turbidity
reduction, 98% of TSS removal was achieved. Parmesh et al. (2010) conducted
a batch coagulation study using various coagulants it was reported that
polyaluminium chloride reduced COD by 83% and color by 92% and using
aluminium chloride, it was reported that COD removal was 72% and color
removal was 84%.
Mahesh et al. (2006) investigated the electrochemical degradation of
agro – based paper mill wastewater (black liquor). It was found that the color
removal was 90%.Tong (1999) and Ganjidoust (1997) carried out a
comparative study of horseradish peroxide (chitosan) and other coagulants such

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).

2.3.5.1 Activated Sludge Process


This aerobic biological treatment consists of an aeration tank with
complete mixing followed by a secondary clarifier. Oxygen is provided to the
aerobic microorganisms through aeration. The microorganisms come in contact
with dissolved organic matter in the wastewater, adsorb this material, and
ultimately decompose the organic material to CO2, H2O, some stable
compounds, and more microorganisms. When most of the organic material,
which is food for microorganisms, has been used up, the microorganisms are
separated from the liquid in a settling tank, sometimes called a secondary or
final clarifier. The microorganisms remaining in the settling tank has no food
available, become hungry, and is thus activated; hence the term activated
sludge. The settled microorganisms, now called return activated sludge, are
pumped back to the head of the aeration tank where they find more food in the
organic compounds in the liquid entering the aeration tank from the primary
clarifier, and the process starts over again. Activated sludge treatment is a
continuous process, with continuous sludge pumping and clean water
discharge.
Pranaven et al., (2005) conducted batch studies on two types of activated
o o o
sludge at 40 C, 50 C and 60 C and it was found that the COD removal was
55.2%, 37.3% and 31.4% respectively. Belem et al., (2008) conducted a study
to promote the degradation of organic matter and remove color by contacting
fungi Pleurotus sajor caju or P. ostreatus with effluents from Kraft pulp mill
after treatment by an activated sludge process. The maximum COD removal is
83%.
Mohseni et al., (2004) investigated to treat the wastewater from an
industrial milk factory using bench scale aerobic Sequencing Batch Reactor
(SBR).The reactor was constructed from plexiglass material and its volume was
22.5 L. The COD removal efficiency was achieved more than 90%, whereas
COD concentration varied from 400 to 2500 mg/L. The optimum dissolved
oxygen in the reactor was 2 to 3 mg/L and MLVSS was around 3000 mg/L.

Control of nutrients, low loading rates, introduction of equalization basin


is the process control parameters for successful treatment. Two common
operational problems encountered during the treatment of pulp and paper waste
waters in activated sludge plants are limiting concentrations of nitrogen and
phosphorus for the maintenance of microbial population and growth of
filamentous organisms or formation of pinpoint flocs that impact the sludge
settling rates thereby reducing the effluent quality.
The problem of nutrient deficiency is to overcome through the external
addition of nutrients with optimization of their dosage. But it required
extensive monitoring of treated effluents for N and P prior to discharge to avoid
adverse environmental impacts such as eutrophication of receiving waters.

2.3.6 Advanced Oxidation Process


Advanced oxidation processes (AOPs) are used to oxidize complex
organic constituents found in wastewater that are difficult to degrade
biologically into simpler end products. It involves the generation and use of
hydroxyl free radical (HO˙) as a strong oxidant to destroy compounds. They are
nonselective in their mode of attack and able to operate at normal temperature
and pressures, capable of oxidizing almost all reduced materials without
restriction to specific classes or groups of compounds, as compared to other
oxidants. The hydroxyl radicals once generated can attack organic molecules by
radical addition, hydrogen abstraction, electron transfer and radical
combination. Advanced oxidation processes are also able to improve the
biodegradability of the contaminants through converting recalcitrant
contaminants into smaller and consequently more biodegradable intermediates.
The generation of hydroxyl radicals involves the combination of

oxidants, such as H2O2 or O3 with UV radiation or a catalyst. The formed


radicals react with organic materials breaking them down gradually in a
stepwise process. Destruction of pollutants in pulp and paper effluents may be
achieved by advanced oxidation methods such as Photo catalysis (titanium
dioxide/ hydrogen peroxide), Photo-oxidation using hydrogen peroxide
(H2O2/UV), Ozone (O3)/UV systems, Fenton type reactions, Wet oxidation,
employing strong oxidants such as ozone.

2.3.6.1 Photocatalysis
Photo catalysis is carried out in an irradiated reactor that contains a

semiconductor, generally TiO2. The semiconductor absorbs the radiant energy


of wavelength corresponding to its band gap generating a couple’s of electron-
hole. This couple acts as an oxidation-reduction system on the surface of the
semiconductor, destroying the organic compounds.
Adish and Kanmani (2010) treated the phenolic wastewaters by means
of H2O2-promoted TiO2 photocatalysis in a single baffle reactor. It was
reported that the degradation of phenol with solar/ TiO 2/H2O2 process is two to
three times faster than solar/TiO 2 process. Solar photocatalytic treatment of 4h
enhanced the biodegradability value from 0 to 0.44.

2.3.6.2 Photo – Oxidation Systems


Photo – oxidation systems using H 2O2/UV or O3/UV, combinations
generate hydroxyl radicals that are short lived but powerful oxidizing organics
through hydrogen abstraction. It results in the total destruction of refractory
organics without generation of sludges or residues.
The most accepted mechanism for the photolysis is the rupture of the O-
bond by means of ultraviolet light forming two hydroxyl radicals.
H2 O2 2OH˙ ……. (2.1)
2.3.6.4 Wet Oxidation Process
Wet air oxidation (WAO) has proved to be an effective method for the
treatment of effluents containing high organic matter content and toxic
chemicals. Several homogenous and heterogeneous catalysts have been used
for the WAO reaction.
Anurag Garg (2004) described the wet air oxidation of pulp and paper
mill effluent for the removal of non-biodegradable and toxic compounds using
heterogeneous catalysts. A maximum COD reduction of 83% for (CuO-

ZnO/CeO2) was obtained in 2 h reaction time.

2.3.6.5 Fenton process


Among advanced oxidation processes, Ferric reagent has been used as
the chemical process for wastewater treatment and pre-treatment. Fenton
system is one of the most interesting oxidative techniques for the abatement of
refractory and toxic organic pollutants in wastewater. The high removal
efficiencies of this technique can be explained by the formation of hydroxyl
3+ 3+
radical (HO˙) and oxidation of TiO 2 to Fe .Both TiO2 to Fe are coagulants,
so the Fenton process can, therefore, have dual function, namely oxidation and

coagulation, in the treatment processes. The usefulness of TiO 2/ H2O2 as an


oxidant for wastewater treatment is attractive due to the facts that i) iron is a
highly abundant and non-toxic element, and ii) hydrogen peroxide is easy to
handle environmentally.
Fenton processes comprise a group of processes characterized by the
addition of an iron catalyst in order to improve the results of the advanced
oxidation. The ferrous salts combined with hydrogen peroxide under acidic
conditions. The mechanism of these processes is based on the generation of

hydroxyl radical by the catalytic decomposition of H 2O2 in acidic medium and


catalyzed by iron salts given by the following equations..

SOLOR PHOTO CATALYSISTS

Slaughterhouse effluent has the additional problem of its great variability in


composition and concentration, not only from one day to another, but even over the
course of a single day according to the operations being carried out at any given time
The meat processing industry uses 24% of the total freshwater consumed by the food
and beverage industry and up to 29% of that consumed by the agricultural sector
worldwide .
Anaerobic digestion is the preferred biological treatment that is applied in
slaughterhouse wastewater treatment due to its effectiveness in treating high strength
wastewater. Although anaerobic treatment possesses great advantages, it hardly
produces effluents that comply with current discharge limits and standards. Generally
speaking, although anaerobic treatment is an efficient process, the slaughterhouse
wastewater organic strength makes it difficult to achieve complete stabilization of the
organic compounds.
The dairy industries, which produce a derivative highly polluting whey or dairy serum,
are also among the food industries generating the highest quantity of waste. Dairy
serum is defined as a milk fraction, of any species, that does not precipitate because of
the action of rennet or because of the acids during the cheese-making process. The
main contributors of organic load to these effluents are carbohydrates, proteins and
fats originating from the milk.

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

Poultry feather is a challenge to anaerobic digestion because it degrades poorly under


anaerobic conditions (reviewed by Bourne, 1993). Feather consists mainly of keratin,
a fibrous protein, and it is the tight packing of the protein chain into a supercoiled
polypeptide chain with a high degree of cross-linking by cystine disulphide bonds,
which is mainly responsible for its poor degradability (reviewed by Bourne, 1993).
Friedrich and Antranikian (1996) isolated an anaerobic bacterium, thermophilic
Fervidobacterium pennavorans, that is capable of degrading native feather, and
Williams and Shih (1989) isolated and characterised a featherdegrading bacterium,
Bacillus licheniformis, from a digester treating manure and poultry feather (Williams
et al., 1990). The latter bacterium, though isolated from an anaerobic habitat, grew
maximally under aerobic condition, but its cell number declined slowly under
anaerobic condition. Besides, the bacterium could degrade only autoclaved feather.
Various pre-treatments have been shown to improve the nutritive value of feather for
animal feed (El Boushy and van der Poel, 1990; Onifade et al., 1998; Papadopoulos,
1985). Several pre-treatments to increase the methane yield of feather were tested
(Salminen et al., submitted). Combined thermal (120 _C, 5 min) and enzymatic
(commercial alkaline endopeptidase, 2–10 g/l) treatments increased its methane yield
in the range of 37–51%, whereas thermal (70–120 _C, 5 min–1 h),
chemical (NaOH 2–10 g/l, 2–24 h), and enzymatic treatments were less effective in
yielding methane, increasing in the range of 5–32%.
HRT of 50 days and showed a methane yield of 0.55 m3of methane/kg VSadded
(Table 2). However, both HRT and loading were highly significant for the
performance of the process. At a loading of 1.0–2.1 kg VS/m3 d and a HRT of 12.5–25
days, the process appeared inhibited, as indicated by the accumulation of LCFAs and
the declined methane yield (Salminen and Rintala, submitted). Accumulated LCFAs
were proposed to be the main factor affecting the recovery of the process from
inhibition (Salminen et al., submitted). Furthermore, the simulation model showed that
the degradation patterns of solid poultry slaughterhouse waste involved complicated
feedback connections, suggesting that the inhibition of propionate degradation by
LCFAs and the inhibition of hydrolysis by a high propionate concentration
constituted the rate-limiting step in the degradation of the waste in batch assays
(Salminen et al.,2000). Webb and Hawkes (1985a) described a practicable treatment of
poultry litter in mesophilic digesters (Table2). Anaerobic treatment of poultry manure
has been proven feasible as well (Table 2) (Barik et al., 1991;Webb and Hawkes,
1985b), though ammonia inhibitionmay cause difficulties in the process (Hunik et al.,
1990; Krylova et al., 1997; Pechan et al., 1987; Webb and Hawkes, 1985b). A
complete degradation of up to 20 g/l of sheep tallowwas shown in batch digesters
under mesophilic conditions in ca. 90 days of incubation (Broughton et al.,1998).
Under thermophilic conditions, though, and with
a substrate concentration of 5 and 10 g/l, methane production was delayed by 43 and
48 days, respectively, and 20 g/l of tallow showed no methane production
within 90 days of incubation. In these studies, LCFAs and VFAs accumulated
considerably but were finally degraded to biogas, except in the thermophilic study
with a tallow concentration of 20 g/l. Banks and Wang (1999) investigated the
treatment of cattle blood and rumen paunch contents in a twophase
process with uncoupled solids and liquid retention times. Compared to a single stage
process, the two-phase process allowed a higher overall loading,
3.6 kg TS/m3 d, with acceptable performance (Table 2). In the first phase of the
process, hydrolysis was apparently enhanced owing to the hydraulic flush, which
prevented the accumulation of intermediates, the potential inhibitors of hydrolysis
(Banks and Wang, 1999).Chen and Shyu (1998) investigated the anaerobic
treatment of poultry mortalities in a combined UASB reactor and a leach bed. An 86%
TS reduction and a methane yield of ca. 0.20 m3=kg of wet weight of mortalities were
achieved in 118 days (Chen and Shyu,1998). Chen (1999) showed a methane yield of
0.25 m3/kg of wet weight of mortalities in a process in which
three leach beds were connected to one UASB in analternating fashion. The
degradation of one batch of mortalities took about 62days.
5.3. Co-digestion Co-digestion of wastes with varying characteristics is one way to
dilute toxicants and to supply missing nutrients and a suitable moisture content
(reviewed by Mata-Alvarez et al., 2000). However, transport costs and
various policies of waste producers may limit the use of
this process (reviewed by Mata-Alvarez et al., 2000).A mesophilic laboratory-scale
digester, treating poultry slaughterhouse waste together with waste from a food
packing plant and inoculated with mesophilic digested sewage sludge could handle
loads up to 4.6 g VS/l

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.

2.4.2 Studies on Aerated Lagoons


S.N. Liss and D.G. Allen (1992) conducted a microbiological study by
subjecting the pulp mill aerated lagoon to the changing composition of the
effluent and variations in climate. It was found that organo chlorine removal
was found not to vary seasonally. The BOD removal across the lagoon was
consistently greater than 80%.
2.4.3 Studies on Anaerobic Treatment Processes
An anaerobic process is considered more suitable to treat high strength
organic effluents. High rate reactors typically achieve 80 - 90% reduction in
3 3
BOD5, with biogas and methane production of 0.5 m /kg COD and 0.35 m /kg
COD respectively. Biomass generation ranges from 0.05 – 0.1 kg VSS/kg COD
removed.

2.4.3.2 Anaerobic Filter


Perez et al. (1998) reported that in anaerobic filter, 50% organic removal
efficiency was obtained on corrugated plastic tubes.

2.4.4 Studies on membrane filtration


Shukla et al. (2009) treated the E – stage (extraction stage) bleach plant
effluent in the ultra filtration and nanofiltration from the point of view of
system closure. By ultra filtration, the COD and color removal was reported as
71% and 81 % respectively.TDS removal was only 40.53%.AOX removal was
61.91% and chromium removal was 95.45%.After nanofiltration, the COD and
color removal was 78.58% and 95.78% respectively.TDS removal was 52% and
AOX removal was 78.39%.
2.5 STUDIES ON COUPLED TREATMENT PROCESSES
In order to improve the quality of treated Slaughterhouse effluents,
integrated methods that often require a combination of biological and
physicochemical treatment methods.
Guiot et al. (1993) conducted anaerobic/aerobic sequence for the
degradation of toxic compounds, mainly chloro organics. Shuizhou et al. (2005)
studied two phase anaerobic degradation for wastewater treatment with
anaerobic reactors. Marcia et al. (2009) investigated the removal of COD, TOC,
total phenols and color using combined activated sludge processes and single
processes. It was found that the combined activated sludge
– O3 at pH 10 can remove around 80% of COD, TOC and color from Kraft E1
effluent. Akmehmet et al. (2006) conducted a research on the integrated process
for the treatment of bleached Slaughter effluents. It was reported that the AOX
removal was 87%.
Natasa et al., (2008) treated the winery wastewater subjecting to Ferric
coagulation oxidation resulting in 80% of COD or BOD removal after 4 hours
of reaction time. About 95% of COD was removed by combined biological and
Ferric coagultion oxidation. Although different biological treatment methods
such as activated sludge, lagoons or anaerobic processes, are being used to
reduce the organic content before wastewater is discharged into receiving
water, the color from lignin derived products remains almost unaltered.
Moreover, chlorinated organic compounds are only partially removed by
biological wastewater treatment. In recent studies certain fungi and a mixed
culture of algae were used to degrade the lignin derived chlorinated and non-
chlorinated compounds, hence color and AOX content of wastewater can be
reduced. However, high glucose requirement of the microorganisms is the
major drawback of fungal treatment and the strong brown color of
Slaughterhouse effluent reduces the metabolic activity of algae in the treatment
process. Therefore coupled treatment processes are employed. Advanced
oxidation
process is used as a pre treatment to increase the biodegradability followed by
the biological treatment.
From the table 2.1, it is concluded that using biological methods, it takes
about 3 to 7 days to treat the Slaughterhouse wastewater. Usually, wastewater is
treated in aerated lagoons and activated sludge which reduce chemical oxygen
demand, biological oxygen demand but are not very efficient. They need
upgradation of activated sludge whereas using advanced oxidation processes; it
takes only 2 to 3 hrs to treat the wastewater. The maximum COD removal is
achieved in physico-chemical, AOP and Ferric per oxidation and coagulation,
when comparing with the detention time, using Ferric reagent, within very short
duration maximum COD removal can be achieved.

Table 2.1 Performance of various treatment processes

Type of treatment Removal Detention time


efficiency

Physico-chemical COD – 95.2% 2 hrs

Advanced oxidation process(Fenton’s COD – 90% 10 min


reagent)

Fenton’s peroxidation and coagulation COD – 90% 2 hrs


Color – 100%

Biological treatment COD – 75% 7 days


Color – 83%
Lignin – 75%
Phenol – 85%

Thus, Photo catalysts reagent could be used in combination with


biological process in order to reduce the toxicity, and to improve the
biodegradability, odor and color removal.
CHAPTER 3

MATERIALS AND METHODS

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.

3.2 COLLECTION AND CHARACTERIZATION OF


SLAUGHTERHOUSE WASTEWATER
The wastewater samples were collected from the Slaughterhouse located
near Cheranmahadevi and the initial characteristics of wastewater was done by
the standard methods. The table 3.1 shows the analysis methods for the
characterization of experimental parameters. The figure 3.1 shows the
schematic methodology of Ferric coagulation process.

Table 3.1 Analysis methods for the treatment of Slaughterhouse


wastewater

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

Collection and characterization of wastewater (pH, COD, color, TSS, BOD)

Fabrication of lab scale photo- Fenton reactor


• Batch reactor
• Volume – 8 L
• Size - 21.5 cm x 21.5 cm x 15 cm

Operating parameters
ƒ pH - 2 to 4

ƒ TiO2 - 0 to 1.5 g/L


ƒ H2O2 - 0 to 25 g/L
ƒ Solar irradiation time –1 hr COD and
ƒ Liquid depth, biodegradability Color

Kinetic study

Design of Pilot plant reactor

Cost analysis

Figure 3.1 Schematic methodology of Ferric coagulation process


3.3 MATERIALS
Phosphate buffer solution, magnesium sulfate, calcium chloride, ferric
chloride, manganese sulfate, a lkaliiodi deazide, concentrated sulphuric acid,
sodium thiosulfate, starch indicator, potassium dichromate, mercuric sulfate,
ferrous ammonium sulfate, ferroinindi cator, analytical grade iron sulphate

(FeSO4.7H 2O), and hydrogenper oxide (Merck) were used.

3.4 EXPERIMENTAL M ETHODS


Th e figure 3.2 shows the Ferric coagulation batch reactors made of
Plexiglas . The Pho to – Fento n reactions were carried out in a seven liter batch
reactor with the working volu me of 2 L. The whol e system was exposed under
strong sol ar irradiati on, from 12.00 am to 1.00 pm from January to April. When
the system was expo sed to the sunlight; it was recorded as the beginning of the
experimen t. The sa mple was taken from the react or for every five minutes to
analyze COD and the color was monitored in the ab sorbance range of 475 nm.
3.5 EFFECT OF OPERATING PARAMETERS
The effect of operating parameters such as pH, ferrous ion, hydrogen
peroxide, irradiation time, liquid depth and biodegradability were analyzed.

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.

3.5.2 Effect of TiO2concentration

The effect of TiO2 concentration on the decolorization and COD


removal has been studied. During the optimization of , the concentration of

TiO2 was varied in the range of 0 to 1.5 g/L with the optimum pH and the

dosage of H2O2 as 15 g/L. The wastewater sample of volume 2 L was taken in


the reactor. Hydrogen peroxide and ferrous sulfate were added and stirred well.
Then the photo-Fenton 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 color and COD.

3.5.3 Effect of H2O2 concentration

The degradation of COD and decolorization were studied by varying the


dosage of H2O2 in the range of 0 to 25 g/L with the optimum value of pH and
the concentration of TiO2. The wastewater sample of volume 2 L was taken and
with this, ferrous sulfate and hydrogen peroxide were added and stirred well.
The photo-Fenton reactions were carried out for one hour under strong solar
radiation from 12.00 pm to 1.00 pm. The sample was taken for every five
minutes and the removal of color and COD were analyzed by standard
methods.

3.5.4 Effect of liquid depth

To study the effect of liquid depth, different volumes of wastewater


samples were taken in the reactors. The depth was varied as 1.15 cm, 2.3 cm,
4.6 cm, 7.2 cm, 9.7 cm and 12.2 cm. The depth plays an important role in the
degradation of COD. The volume of wastewater samples taken were 1 L, 2 L, 3
L, 4 L, 5 L and 6 L. These samples were taken in the reactors and ferrous
sulfate and hydrogen peroxide were added and stirred well. The system was
exposed to sunlight for one hour from 12.00 pm to 1.00 pm. The samples were
taken for every five minutes and the COD and decolorization were analyzed by
standard methods.

3.5.5 Effect of biodegradability

The Slaughterhouse wastewater is non - biodegradable in nature and


they contain recalcitrant compounds. Significant enhancement of

biodegradability was studied using solar/ TiO 2/H2O2.The experiment was


carried out in the batch reactor of volume 7 L with the working volume of 2 L
for 1 hour. The samples were taken for every 10 minutes and it was analyzed
for BOD and COD. The biodegradability of the wastewater was evaluated by
BOD/COD ratio.
3.6 SOLAR PHOTO-FENTON DEGRADATION KINETICS

The kinetic study of the Ferric coagulation process was investigated by

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.

3.7 DESIGN OF PILOT PLANT REACTOR AND COST ANALYSIS

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

RESULTS AND DISCUSSION

4.1 GENERAL

The wastewater from Slaughterhouse wastewater was investigated in the


following study. Lab scale Ferric coagulant reactors were used for the reactions
to be carried out. COD and BOD were analyzed using standard methods and
the color was monitored using visible spectrophotometer.

4.2 CHARACTERIZATION OF SLAUGHTERHOUSE


WASTEWATER
The initial characteristics of sample wastewater were analyzed by
standard methods given in table 4.1

Table 4.1 Initial characteristics of Slaughterhouse wastewater

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.

Table 4.2 Effect of pH on color removal

% 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

The effect of pH on degradation of COD is shown in figure 4.2. The


COD reduction increases rapidly as the pH increases from 2 to 4. At a reaction
higher than pH 5, it has been found that the COD removal decreases. This is
because the ferrous catalyst was inactivated with the formation of ferric hydro

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

TiO2 in Fenton’s oxidation (Malik et al., 2003).

105

100
%color removal

95

pH3
90 pH2

pH4
pH5
85
pH6
pH7

80
5 10 15 20 25 30
Time (min)

Figure 4.1 Effect of pH on color removal

Table 4.3 Effect of pH COD removal

Parameter COD (mg/L) % COD removal


pH2 90 95.8
pH3 75.8 96.4
pH4 81.25 96.5
pH5 739.2 65.3
pH6 806.4 62.2
pH7 873.6 59
100

95

90

85
% COD
removal 80

75

70

65

60

55

50
pH2 pH3 pH4 pH5 pH6 pH7

Figure 4.2 Effect of pH on COD removal

Worawit et al., 2009 observed that the degradation of Disobutyl Pthalate


(DIBP) decrease with decreasing pH when the solution pH was lower than 3.He
observed the optimum pH to be at 3. At low pH, the hydrogen peroxide became
+
stable probably because it solvates a proton to form an oxonium ion (H3O) .An

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

The degradation of organic compounds and the removal of color were

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

of COD increases as TiO 2 increases. Maximum COD reduction occurs when

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 .

Table 4.4 Effect of TiO2 on color removal

% 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

Further addition of iron becomes inefficient. The increase in


decolorization and COD removal was due to the production of hydroxyl

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)

Figure 4.3 Effect of TiO2 on color removal

Barbusinski et al., (2001) reported that the removal of organophosphorus


pesticides ie., fenitrothion (from 98.5 to 100%) and chlorfenvinphos (from 97.1
3
to 100%) with the average value of TiO2 = 3.2 µg/dm .

Table 4.5 Effect of TiO2 on COD removal

TiO2 concentration (g/L) COD (mg/L) % COD removal


0 500 76.3
0.5 288 86.5
1.0 110 94.8
1.5 127 94
100

95

% COD 90
removal

85

80

75

70
0 0.5 1 1.5

TiO2 concentration (g/L)

Figure 4.4 Effect of TiO2on COD removal

4.3.3 Effect of H2O2 concentration

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

degradation of COD and decolorization increases as the concentration of H 2O2


increases until the critical concentration is achieved. Above this critical
concentration, the degradation of COD and decolorization decrease as a result
of scavenging effect explained by the following equations..

˙
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)

Figure 4.5 Effect of H2O 2 on color removal


The results are shown in table 4.6 and 4.7. It is clear from the figure 4.5
and 4.6 that the increasing amount of H2O2 leads to greater COD and color
removal. There was a small difference between the COD removal with 5 g/L,
10 g/L and 15 g/L of H2O2 dosage. Therefore, it was not worth taking large
amount of H2O2 dosage for increasing degradation. Hence lower dose of 5 g/L
of H2O2 was taken as the optimum dosage. Further increase in H2O2
concentration lowered the degradation rate. This is because of the excess H 2O2
reacts with the hydroxyl radicals earlier formed and hence acts as an inhibiting
agent of degradation by consuming the hydroxyl radicals responsible for
degrading the pollutant molecule (Ghaly et al., 2001).

Table 4.7 Effect of H2O2 on COD removal

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)

Figure 4.6 Effect of H2O2 on COD removal

4.3.4 Effect of liquid depth


In order to study the effect of liquid depth, different volumes of
wastewater samples were taken in the reactors and the chemicals such as

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.

Table 4.8 Effect of liquid depth on COD removal

Depth (cm) COD (mg/L) % COD removal


2.3 190 91
4.6 245 88.5
7.2 330 84.5
9.7 550 74
12.2 639 70

100

95

90
% COD
removal 85

80

75

70

65

60
2.3 4.6 7.2 9.7 12.2
Depth in cm

Figure 4.7 Effect of liquid depth on COD removal


4.3.5 Effect of biodegradability

To study the biodegradability of wastewater, the wastewater sample of


volume 2 L was taken and the chemicals such as ferrous sulfate and hydrogen
peroxide were added at pH4. 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 ten minutes to analyze COD and BOD. The results are shown in the
table 4.9.The BOD/COD ratio of untreated wastewater sample was 0.028.When
the BOD/COD ratio is above 0.4; it indicates a readily biodegradable
wastewater. The solar photo-Fenton process enhanced the biodegradability to
0.83 after 60 minutes of irradiation time. It is clear from the figure 4.8 that
within 40 minutes, the BOD/COD ratio reached the value of 0.45.

Table 4.9 Biodegradability of pulp and paper mill wastewater

Time (min) BOD/COD


0 0.028
10 0.09
20 0.13
30 0.23
40 0.45
50 0.62
60 0.83

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)

Figure 4.8 Biodegradability of pulp and paper mill wastewater

4.4 SOLAR PHOTO-FENTON DEGRADATION KINETICS

The kinetic study of the solar photo-Fenton process was investigated by

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

times faster than solar/ TiO2 process.

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

solar/H2O2 0.011 0.92

solar/TiO2 0.07 0.77


solar/TiO2/H2O2 0.94

4.5 DESIGN OF PILOT PLANT REACTOR AND COST ANALYSIS

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

land use treated effluent secondary SBR

clarifier

Figure 4.9 Proposed treatment layout of Slaughterhouse wastewater


CHAPTER 5

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

In this study, it has been found that ferric coagulant is an appropriate


process for the pretreatment of slaughterhouse wastewater. The optimum pH for

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.
REFERENCES

1.USEPA. Development document for the proposed effluent limitations guidelines and
standards for the meat and poultry products industry. Office of Water (4303T), Unite
States Environmental Protection Agency (USEPA), EPA-821-B-01007, 2002.

2. Council of the European Communities. Council Directive on health problems


affecting the production and marketing of meat products and certain other products of
animal origin. Official J. Eur. Comm. 1977, L 026 (31 October 1977), 0085–0100.

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