Professional Documents
Culture Documents
COMSATS Institute of Information Technol
COMSATS Institute of Information Technol
By
Zulfiqar Ahmad Bhatti
SP05-R67-003
Ph.D. Thesis
i
COMSATS Institute of Information Technology
A Thesis Presented to
In partial fulfillment
Ph.D.
(Environmental Sciences)
By
CIIT/SP05-R67-003/ABT
March, 2011
ii
Low Cost Municipal Wastewater Treatment
Supervisor
iii
Final Approval
This thesis titled
Low Cost Municipal Wastewater Treatment
By
Zulfiqar Ahmad Bhatti
Supervisor: ________________________________________________
Dr. Iftikhar Ahmad Raja
Foreign Professor
Dean: ________________________________________________
Prof. Dr. Arshad Saleem Bhatti
Dean (Faculty of Sciences)
iv
Declaration
I Zulfiqar Ahmad Bhatti hereby declare that I have produced the work presented in this
thesis, during the scheduled period of study. I also declare that I have not taken any
material from any source except referred to wherever due. If a violation of HEC rules
on research has occurred in this thesis, I shall be liable to punishable action under the
plagiarism rules of the HEC.
(CIIT/SP05-R67-003/ABT)
v
Certificate
It is certified that Mr. Zulfiqar Ahmad Bhatti has carried out all the work related to this
thesis under my supervision at the Department of Environmental Sciences, CIIT
Abbottabad.
Supervisor:
CIIT Abbottabad
Submitted through:
vi
DEDICATION
&
vii
ACKNOWLEDGEMENTS
It’s really hard to express my feelings upon achieving the biggest milestone in my life.
The first and profound gratitude goes to Almighty Allah. All praises for Almighty
Allah- the most benevolent, ever merciful and compassionate, the creator of universe
who awarded me strength, good health and confidence throughout my endeavor. I
extend my humblest and enthusiastic words of thanks to His Holy prophet Muhammad
(Blessing and peace be upon him) who is forever source of light and guidance for all
the humanity.
I would like to extend my sincere gratitude to the CIIT research grant Islamabad for
young scientist who provided funds for research to complete PhD.
I am cordially thankful to Dr Qaisar Mahmood for his kind help in start up of up flow
anaerobic sludge blanket reactor. I wish to express my cordial thanks and gratitude to
all individuals and COMSATS institute of information technology Abbottabad that
have contributed to make this study a success and make this dissertation possible.
Especial thanks to Ir Prof Dr Willy Verstraete, Ghent University Belgium, who
suggested me to study this treatment option.
viii
laboratory attendants Saboor, Maroof and Naeem facilitating in handling equipments
and collection of samples.
ix
ABSTRACT
Chemically enhanced primary treatment was first tested in the research to select best
coagulant to reduce the pollutant load of MWW. Various coagulants viz. FeCl3,
Moringa oleifera seed extract and alum were compared for their suitability to treat
MWW. Different concentrations (4~32 mg L-1) were applied in a series of batch
treatment process mode at 600-620 rpm stirring for five minutes. It was observed that
alum was effective in reducing the chemical oxygen demand (COD) up-to acceptable
level but above the optimized dose of alum total dissolved solids (TDS) were found
increasing at greater extent. There was an increase of TDS when the level of alum was
increased above the optimized value of 32 mg L-1. The highest rate of pollutants
removal load was observed when 22 to 30 mg L-1 of alum was used. Therefore, alum
concentration in the range of 22 to 30 mg L-1 was an optimum dose for MWW
treatment. Removal of COD and Ortho-Phosphorus can be possible with increased
dose of alum but the cost of alum and increase of TDS shows less relatively favorable.
x
municipal waste. The drawback in this regard, infrequent supply of waste H2O2 from
industry can stop the treatment process.
Some industries were selected to treat their wastewater. Carwash industry was
one of them whose effluent was not studied often. This wastewater contained high
content of oil 83 mg L-1 and COD >1000 mg L-1. Due to presence of oil it was not
feasible to treat directly with alum or H2O2. Therefore aeration was added as
pretreatment step to bring oil content to the surface where it was scraped out from
aeration tank. Effluent from aeration tank was further treated with alum in second step
and H2O2 at third step. Treatment efficiency was 96% oil, COD, turbidity and TDS
were reduced upto 93%, 94% and 74%, respectively. The present approach was proved
cost effective and requires less space without any pH control. Only costly factor was
aeration to separate the oil, other than aeration it can be more expensive to separate.
Thus the treatment process can be applied on pilot scale to further evalute its
efficiency.
The present study also compared the effectiveness of used and fresh H2O2 to
treat the domestic waste and to reduce the alum dose for chemical sedimentation. It
was observed that used waste 40% H2O2 was very effective and economical. Fresh
35% H2O2 can be purchased Rs 40/L from the market but used waste 40% H2O2 can be
obtained only from specific industries where it used for disinfection. Using 40% waste
H2O2 was found very effective to reduce COD, turbidity and microbial load. An
addition step was merged into H2O2 was ultra violet (UV) light to speed up the
reaction. The proposed system was consists of two major step where first sediments
was settled down with alum and decant from first step was used to treat with H2O2 and
UV in the same tank. This proposed system was effective (p < 0.05) to treat domestic
wastewater but carwash and food industry wastewater may require other treatment
steps need to be added. The combination of H2O2 with UV light was found very
effective (p < 0.05) to decrease BOD, COD, and turbidity and coliform bacteria in
MWW. Waste H2O2 generated from an industrial process of disinfection was found
more effective in the treatment of domestic wastewater than fresh 35% H2O2. The
waste H2O2 can be applied in combinations with UV light to treat domestic wastewater
effectively.
The UASB reactor was used to treat mixed MWW at hydraulic retention time
24-48 hrs and at an average temperature 25-34ºC. The aim was to test two stage
xi
treatment concept for low cost MWW treatment as UAB in first stage and waste H2O2
40% 2 ml L-1 of UASB effluent at second stage. Moreover, the effect of
micronutrients on the treatability of UAB was also investigated. After start up with
glucose for first 15 days (first stage), the reactor was fed with macro and
micronutrients synthetic nutrients influent (SNI) for 45 days (second stage). The
maximum substrate removal rate was same 0.07 d-1 for both glucose and SNI. Removal
efficiency of total suspended solids (TSS), COD, total nitrogen (TN), ortho phosphorus
(Ortho-P) and Turbidity as 73%, 99%, 84%, 19% and 67%, respectively. Waste H2O2
was found successful in NH4+ removal during post treatment where 80% nitrogen was
removed. Low cost integrated treatment using UASB and H2O2 was found an excellent
novel treatment choice for mixed MWW in developing countries.
Key words: Upflow anaerobic sludge blanket, advanced oxidation process, chemically
enhanced primary treatment, national environmental quality standards.
xii
Table of Contents
xiii
2.6 CHEMICALLY PRIMARY TREATMENT OF WASTEWATER ........................................ 25
2.6.1 Financial benefits of CEPT ............................................................................................... 26
2.6.2 Efficiency of organic and inorganic coagulants ............................................................... 26
2.7 OILY WASTEWATER TREATMENT WITH COAGULATION/FLOCCULATION ............. 29
2.8 USE OF CEPT SLUDGE AS ADSORBENT .................................................................. 29
2.9 EFFECT OF POLYMERIC FLOCCULENT PRODUCED FROM PLASTIC WASTE ............ 30
2.10 COMBINE CHEMICAL AND BIOLOGICAL LOW COST TREATMENT SYSTEMS .......... 31
2.11 ADVANCE OXIDATION PROCESSES IN MUNICIPAL WASTEWATER TREATMENT.... 33
2.11.1 Municipal wastewater treatment with H2O2 ................................................................ 34
2.11.2 Fenton reagent in AOP ................................................................................................. 35
2.11.3 Textile effluent treatment with AOP ........................................................................... 36
2.12 SLUDGE DIGESTION WITH H2O2.............................................................................. 36
2.13 ANAEROBIC TREATMENT OF MUNICIPAL WASTEWATER TREATMENT.................. 37
2.13.1 Hydrolysis..................................................................................................................... 38
2.13.2 Acetogenesis and Acid Formation ............................................................................... 38
2.13.3 Methanogenesis ............................................................................................................ 39
2.13.4 Start up of up flow anaerobic sludge blanket (UASB) reactor ................................... 39
2.13.5 Start up of UASB reactor without inoculation ............................................................ 45
2.13.6 Function of micro-nutrients during start-up of UASB ................................................ 46
2.13.7 Operational data and micronutrient requirement ......................................................... 47
2.13.8 Gas utilization............................................................................................................... 48
2.13.9 Industrial wastewater treatment by UASB .................................................................. 49
2.14 CONCLUSIONS ......................................................................................................... 50
3 Chapter 3: .............................................................................................................. 61
xiv
3.5 CONCLUSIONS ......................................................................................................... 73
4 Chapter 4: .............................................................................................................. 77
5 Chapter 5: .............................................................................................................. 91
xv
Municipal Wastewater Treatment by Physico-Chemical Processes
xvi
8.2 MATERIALS AND METHODS.................................................................................. 147
8.2.1 Wastewater Sample ......................................................................................................... 147
8.2.2 Treatment design ............................................................................................................. 147
8.2.3 Analytical procedures ..................................................................................................... 148
8.3 RESULTS AND DISCUSSION ................................................................................... 149
8.3.1 Use of H2O2 to polish UASB effluent ............................................................................ 154
8.3.2 Comparison with other processes ................................................................................... 155
8.4 CONCLUSIONS ....................................................................................................... 156
xvii
List of Figures
Figure 2.1 CEPS-UASB (Kologo, 1999) ..................................................................... 31
Figure 2.2 Schematic of the low investment sewage treatment concept with zeolite
installation ................................................................................................... 32
Figure 2.3 The UASB reactor ...................................................................................... 42
Figure 2.4 Biological conversions in aerobic and anaerobic systems ......................... 42
Figure 2.5 Anaerobic decomposition of organic matter (Zehnder et al., 1982) .......... 43
Figure 3.1 Location of MWW sampling site in Abbottabad city ................................ 64
Figure 3.2 Decrease in COD after treating with various coagulants ........................... 66
Figure 3.3 Effect of various coagulants on TDS of MWW ......................................... 67
Figure 3.4 Effect of different concentrations of alum on TDS of MWW.................... 68
Figure 3. 5 Effect of alum treatment reaction time on TSS of MWW......................... 69
Figure 3.6 Effect of different concentrations of alum on removal percentage of TSS
from MWW ................................................................................................. 70
Figure 3.7 Effect of different concentrations of alum on removal percentage of TSS
from MWW ................................................................................................. 71
Figure 3.8 Effect of different concentrations of alum on removal percentage of total
kjeldahl nitrogen of MWW ......................................................................... 72
Figure 3.9 Effect of different concentrations of alum on the removal of turbidity in
MWW .......................................................................................................... 72
Figure 4.1 BOD reduction during treatment ................................................................ 82
Figure 4.2 COD removal during treatment .................................................................. 83
Figure 4.3 The variation of BOD/COD ....................................................................... 84
Figure 4.4 COD and turbidity percentage removal ...................................................... 85
Figure 4.5 Changes in pH during treatment ................................................................. 86
Figure 5.1 Schematic diagram of a multi-stage treatment of carwash wastewater ...... 95
Figure 5.2 Effect of aeration on oil contents of CWW ................................................ 96
Figure 5.3 Turbidity reduction of CWW after alum dosing ........................................ 96
Figure 5.4 COD Reduction (mg L-1) of CWW at different application rates of alum . 98
Figure 5.5 Effect of treatment on TDS of CWW ......................................................... 99
Figure 5.6 Effect of treatment on pH of CWW ........................................................... 99
Figure 5.7 Effect of treatment on DO of CWW......................................................... 100
xviii
Figure 5.8 Removal percentage of TDS, COD, Turbidity and Oil contents from CWW
.................................................................................................................................... 101
Figure 6.1 Major steps involved in MWW treatment ................................................ 110
Figure 6.2 Effect of fresh H2O2 treatment on pH with the passage of time ............... 112
Figure 6.3 Decrease in turbidity after treating with alum and H2O2/UV, (Raw WW
represents raw wastewater, NS = Natural Sedimentation) ...................... 113
Figure 6.4 Reduction of COD and BOD after treating with 35% fresh and 40% waste
H2O2 along with UV light (Raw WW represents raw wastewater, NS =
Natural Sedimentation) ............................................................................ 114
Figure 7.1 UASB followed by chemical oxidation with 40% hydrogen peroxide. P1=
peristaltic feed pump, P2 = peristaltic recycle pump ............................... 125
Figure 7.2 pHi (influent), pHe (effluent) comparison during start-up of UASB, using
glucose as a sole nutrient ......................................................................... 126
Figure 7.3 pHi and pHe comparison for synthetic influent used for startup after
addition of micronutrients ........................................................................ 126
Figure 7.4 COD and BOD percentage removal comparison ..................................... 127
Figure 7.5 CODi (influent) and CODe (effluent) comparison................................... 128
Figure 7.6 COD influent and COD effluent form fifteenth day with SNI ................. 129
Figure 7.7 Percent COD removal using SNI in UASB.............................................. 130
Figure 7.8 CODe and Glucose as substrate uptake .................................................... 132
Figure 7.9 Comparison of substrate uptake rate of SNI and glucose......................... 132
Figure 7.10 SNI effects on biodegradable fraction and substrate uptake rate. .......... 133
Figure 7.11 Effects of glucose on Fb and U and substrate uptake rate ...................... 133
Figure 7.12 Effect on ammonium, nitrate and nitrite after treating UASB effluent with
H2O2 ......................................................................................................... 137
Figure 8.1 UASB followed by chemical oxidation with 40% hydrogen peroxide. P1=
peristaltic feed pump, P2 = peristaltic recycle pump ............................... 148
Figure 8.2 COD influent, UASB effluent and H2O2 treated effluent with COD removal
mg L-1. PI =Phase one, PII= Phase two, PIII= Phase three, PIV= Phase
four, PV= Phase five. ............................................................................... 152
Figure 8.3 COD removal efficiency, peroxide COD removal can be considered as total
COD percent removal .............................................................................. 153
Figure 8.4 pH comparison of UASB effluent and H2O2 effluent .............................. 153
xix
List of Tables
Table 2-1 Average composition of domestic sewage (Verstraete, 2004). *DW: dry
weight .......................................................................................................... 18
Table 2-2 Size spectrum for waterborne particle ......................................................... 23
Table 2-3 Comparison of removal efficiencies ............................................................ 27
Table 2-4 Hospital wastewater comparison with urban wastewater ............................ 29
Table 2-5 Main advantages and disadvantages of UASB reactor................................ 41
Table 2-6 Function of macro and micro nutrients in anaerobic digestion ................... 47
Table 2-7 Working goal (NEQS) ................................................................................. 48
Table 2-8 Important parameter for MWW treatment in UASB ................................... 48
Table 3-1 The economic analysis of various treatment options for MWW ................. 74
Table 4-1 Pre-experiment Analysis ............................................................................. 80
Table 4-2 The economic analysis of various treatment options for MWW ................. 87
Table 5-1 Characteristics of the raw car wash wastewater .......................................... 94
Table 5-2 Characteristics of the car wash wastewater before and after the treatment.
*Below Detection Limit ......................................................................... 102
Table 6-1 Pre and post experimental Analysis .......................................................... 109
Table 7-1 Composition of synthetic influent (SNI) ................................................... 124
Table 7-2 Component of trace element solution ........................................................ 124
Table 7-3 Parameters (mg L-1) used to start up UASB reactor .................................. 124
Table 7-4 Standard allowable limits for effluent discharge ....................................... 124
Table 7-5 Average characteristics of raw MWW and effluent of various treatment
steps. BDL = Below detection limit ....................................................... 135
Table 7-6 UASB effluent treatment with H2O2 at optimized dose 2.0 ml L-1 ........... 136
Table 7-7 Comparison of UASB HRT start up with different inoculums ................. 138
Table 7-8 The economic analysis of various treatment options for MWW ............... 139
Table 8-1 Parameters used to treat industrial wastewater .......................................... 148
Table 8-2COD removal comparison, in COD mg L-1................................................ 151
Table 8-3 Treatment efficiency .................................................................................. 152
Table 8-4 Lethal ammonia concentrations at different pH, and its exposure ............ 155
Table 8-5 Treatment efficiency comparison of different investigators treating
carbohydrate type wastewater on the basis of COD percent removal ....... 156
xx
LIST OF ABBREVIATIONS
A Area
NH3 Ammonia
DO Dissolved oxygen
E1 Estrone
E2 17β-estradiol
E3 16 α, 17 β-estradiol
Fb Biodegradable fraction
xxi
MWW Municipal wastewater
NO2- Nitrite
NO3- Nitrate
O3 Ozone
Q Flow rate
SS Suspended solids
TN Total nitrogen
UV Ultra violet
xxii
VSS Volatile suspended solids
V Volume
xxiii
Chapter 1: Introduction
Domestic/Municipal Wastewater Loads/Flow Rates with
Respect to Abbottabad and Pakistan
1
1.1 Introduction
Pakistan’s current population is of 187 million and is expected to grow up to
approximately 221 million by the year 2025 (PDP, 2011; Khan, 2007). The vast
increasing population of Pakistan putting great affect on the water quality which is
required for meeting the industrial, domestic and agricultural needs. Pakistan is
exhausting its water resources and if this is not managed properly then Pakistan will
become water deficit country. Ground water and surface water quality is not
satisfactory and it is continuously deteriorating due to untreated municipal, industrial
wastewater discharge into surface water and usage of insecticides and fertilizers in
agriculture forms. Monitoring the water quality and its management is not sufficient.
Water availability per capita has declined to 1000 m3 from 5,600 m3 (Khan, 2007;
IUCN, 2009).
Water pollution has increased according to different investigators and
surveyors. Polluted water is found more around the big cities and industrial areas.
Deterioration of water quality often caused by synthetic organic toxic chemicals
especially from tanneries, textile industries and municipal wastewater where it causes
spreading of water borne diseases. Sewage treatment is a process of reducing or
removing of contaminants up to acceptable level (Chandio, 1998).
The public water requirement has raised many folds as population is
increasing, industrial growth and bringing more area under cultivation to meet the
increasing demand of agricultural products. All the above factors forced the water
managers to explore the existing freshwater resources. It has been estimated that
about 27% of world’s population do not have access to clean drinking water (Chandio
and Abdullah, 1998).
The conditions become more adverse in developing countries, where there is
lack of resources and the water protection schemes are of least priority. Study by,
Zahid and Baig (1997) concluded that about 80% people living in main cities of
Pakistan lack access to clean potable water. The environmental profile of Pakistan
indicates that about 40% of deaths are related to waterborne diseases spread by water
pollution, mainly due to the sewage and industrial wastewater contamination to
drinking water distribution systems.
Continuing urbanization, growing populations and increasing industrialization
have increased water consumption and correspondingly generating higher volumes of
2
wastewater. Untreated wastewater and poor solid waste management are threats to
human health and natural environment. Regrettably, the public and the private sectors,
in developing countries including Pakistan, are not focusing their attention to the
wastewater treatment practices on domestic and industrial level. Lack of interest in
controlling water born diseases, which causes severe environmental and health
problems. Most of the wastewater is not treated and with the expansion of urban
settlements without wastewater treatment facilities, it will continue to adversely
impact the natural environment and public health. Worst impacts are evident in areas
which are close to industrial sites.
Saeed and Bahzad (2006), reported that more than 28 m3 sec-1 wastewater was
being disposed off in to the River Ravi without any treatment from second largest city
of Pakistan. The river pollution is frequently associated with the disposal of untreated
effluents from municipal, industrial and agricultural wastes and the natural streams
are always considered as an easy way to dispose off many kinds of effluents. The
people’s psychology is that the wastes are washed away and are not visible after
dumping sites.
A study by Balfours (1987) revealed that about 18 m3 sec-1 of wastewater from
Lahore city was being disposed off into the river Ravi and it is estimated that
wastewater flow would increase to 35 m3 sec-1 by the year 2017. This wastewater is
accompanied by a BOD load of 240 mg L-1.
Municipal and industrial wastewater reclamation constitutes a vast potential of
supplementing current and future water supplies. Recent technological advancement
has shown that it is not only practically possible but economically feasible to use
reclaimed water for many purposes including human.
3
COD receiving in municipal wastewater stream. Separate installation of treatment
facility at each source may not be feasible to overcome this problem at present status.
Over a billion people around the world lack access to safe drinking water, with
around 80% of all diseases are due to poor drinking water qualities in developing
countries this lead to 1.7 million deaths annually (UNDP, 1996). In Pakistan, water
availability has already fallen from 5000 m3 per capita to 1,100 m3 in 2005 (IUCN,
2005). According to government statistics, 88% of the districts urban population and
62% of rural residents have access to water supply. But only 33% people have water
supply at their homes and 67% rely on outdoor sources. Water quality analysis report
2005–06, 55% samples were found with coliform contamination (Akram, 2005;
IUCN, 2009).
4
degradation of organic pollutants by microbes, later on these microbes are needed to
be removed prior to discharge. Tertiary treatment is a next step which is advance
treatment option. Some time this treated water is disinfected with chemical or UV
light to reduce microbial load before discharging to wet land or rivers and streams,
where it can be safely used for irrigation purposes in agriculture fields, parks and
green lands (Roland, 1997).
1.3 Pre-treatment
Pretreatment is a process where solids are separated before clogging the pumps
and clarifiers in secondary treatment.
1.3.1 Screening
Sewage wastewater is anxious to eliminate all materials carried in the
wastewater channels. These objects are to remove wood pieces, rags, glass, fruit,
vegetable waste and tampons etc. This can be done by using bar screen, raked bar
screen which commonly used in modern wastewater treatment plant. In small and
common wastewater treatment plants manually cleaning screens are used. Its raking
action can be performed according to deposition of objects on the bar screen and flow
rate. Collected or separated solids are disposed in the land filled areas or incinerated
(Hammer, 2004; Roland, 1997).
5
which moves very slowly 5mm/min speed to collect the sludges and to avoid remix in
above liquid (Hammer, 2004; Roland, 1997).
Roughing filter are used to treat diversified organic loads, such as wastewater
from industries especially food industry where it has high organic load in wastewater.
Wastewater fed into this at very high speed which is designed to face high organic
load as well. Air is required to supply oxygen to create aerobic conditions and to
reduce the odour. During final step biological flock are settle down and this water has
lower level of organic material and suspended matter.
6
production because substrate converted into biogass (Aiyuk, 2004; Ghangrekar, 2005;
Jules, 2011).
In such type of basin aeration provide two functions i) transferring air (oxygen)
for microbial oxidation reaction. Secondly they provide the force to move air and
distributed homogenously and also forcing solid to move and contact with microbes
and oxygen. Typically through this system the air distributed at the rate of 1.8 to 2.7
Kg O2 KW-1h-1. In this system air is not properly mixed as in activated sludge system,
thats reason it is not as efficient as activated sludge system. Oxidation reaction in this
treatment system is very effective when temperature range is 4oC – 32oC and at higher
temperature rate of reaction is high and slow down at lower temperature
(Middlebrooks, 1982; Beychok, 1987).
The great benefit of this system is to control the poor settling of sludge in
“conventional activated system” (CAS). This allow reactor operate at high rate of
“mixed liquor suspended solids” (MLSS) than CAS. The CAS has limitation in sludge
settling due to aeration limitations. The process operate in the range of 8000-12000
mg L-1 MLSS whereas CAS at 2000-3000 mg L-1.
7
In the membrane bioreactor process, the raised biomass concentration allows
very effective removal of soluble and particulate organic biodegradable materials with
higher loading rates. Thus, increased Sludge Retention Times (SRTs) exceeding more
than fifteen days is required to ensure complete nitrification even if the temperature is
cold.
Some kind of similar biological filtration has become trendy in home aquarium
purification as well as filtration. In the system water is cascaded on the wheal of fiber-
mesh before using media filter. This fiber mesh wheel rotates and gets contact with
air, supporting growth of biofilm on the mesh fiber wheel. This can be good system to
remove aquarium waste such as urea and ammonia released by the fish or other
animals in aquarium (Leslie, 1998).
1.6.5 Lagooning
It provides improvement in wastewater quality by providing oxygen through
photosynthesis of macrophytes. These macrophytes create highly aerobic
8
environment. Zooplankton such as daphnia and rotifer play important role in filtering
in lagoon. These species greatly remove the fine particulates (Hammer, 2004).
Constructed wetland is fed in at the inlet and moved in laminar regime through
porous medium until it reaches the outlet zone where it is collected before the outlet.
During this flow regime wastewater is in contact with aerobic, anoxic and anaerobic
zones. Rhizomes and plant roots releases the oxygen and develop aerobic conditions.
Constructed wetlands have long been used for domestic and MWW (Vymazal, 2009;
Cooper et al., 1996; Brix, 2003).
The algae numbers are unsustainable and eventually most of them die. The
overgrowth of algae in aquatic environments causes decrease in oxygen level of the
water due to which most or all of the animals die, which creates more organic matter
for decomposition by bacteria. In addition to deoxygenating, some algal species
produce toxins that contaminate drinking water supplies. Different treatment
processes are required to remove nitrogen and phosphorus. Removal of nutrients has
been studied by different reactors. Sequential batch reactor for biological nutrient
removal from MWW was found very effective in reducing BOD, TSS and ammonium
nitrogen 98%, 90% and 89% at 12 hours cycle time. It consists of a sequencing
operation including the steps of fill, react, settle, decant and idle (Kargi, 2003).
9
nitrate to nitrogen gas. Nitrogen gas is released to the atmosphere and thus removed
from the water.
10
Chemical precipitation of Phosphorus removal can also be achieved by, usually
with salts of iron (e.g. ferric chloride), aluminum (e.g. alum), or lime. This may lead
to excessive sludge productions as hydroxides precipitates and the added chemicals
can be expensive. Chemical phosphorus removal requires significantly (p < 0.05)
smaller equipment footprint, is easier to operate and is often more reliable than
biological phosphorus removal. Phosphorus, in the form of a phosphate rich sludge,
once removed, may be stored in a land fill or reuse in fertilizer (Tchobanoglous, 2003;
Broughton, 2008).
1.7.1 Filtration
Much of the residual suspended matter is removed by sand filter and activated
carbon also removes residual toxins.
1.7.2 Disinfection
Disinfection is a process where microbial population is reduced in water to
safely discharge the treated water into environment. Disinfection efficiency depends
also on raw water quality where to judge the type of disinfection need to be used.
Cloudy water protects microbes against UV light treatment or when contact time is
not sufficient. Low doses of disinfectant and flow rate has substantial effect during
disinfection. Disinfection methods are ozonation, chlorination and UV light.
Chloramine disinfectant is used for drinking water disinfection but not used in
wastewater treatment due to its persistence property in environment. In North
America it is still used for disinfection. It has one disadvantage, reaction between
chlorine and residual organic matter produces carcinogenic compounds chlorinated
organic compounds and these residual are also toxic to the aquatic species. So there is
need to treat treated water with chemical to dechlorinate (Verstraete, 2004).
11
The UV light replaces the chlorine, iodine and other disinfectant. In this
treatment no chemicals are used no byproducts are observed to be hazardous.
Radiation from UV damages the genetic material of virus, bacteria and pathogens.
Only disadvantage of UV lamp is required regular maintenance and proper cleaning
of UV lamp sleeve to allow radiation pas through. It is very important that
microorganisms must not get any protection from UV light (mostly solids left in
pretreatment may provide protection to microbes against UV. The UV light has
become more and more popular in developing countries as well as in developed
countries due to its efficient disinfection and awareness enhanced about chlorination
residual organics in the wastewater and in receiving water body. (IBWA, 1995).
12
1. To select the most effective and locally available coagulant to enhance the
sedimentation of MWW. The dose of selected coagulants [Al2 (SO4)3, FeCl3,
and Moringa oleifera seed extract] were optimized to see the efficient removal
of settle able solids and colloidal particles in the MWW.
2. The study also aimed to explore the effectiveness of used H2O2 (40%) and
alum as integrated treatment to reduce the BOD, COD of MWW and CWW
separately. As MWW in Pakistan also mixed with carwash industry
wastewater. Therefore aim was to explore the possibility of integrated
treatment concept for carwash wastewater to an acceptable level. To discharge
effluent from carwash into drains to contribute less pollution load.
3. To see the best effectiveness of two different application rates (35% and 40%)
of H2O2 during treatment of MWW. The specific objectives in this regard
were to compare the effectiveness of used (40%) and fresh (35%) H2O2 to
treat the MWW.
4. The last part of this research was aimed to evaluate UASB reactor start up
with glucose, synthetic nutrients and its kinetics along with and coupling
effect of UASB and chemical.
13
References
Akram, K., Aslam, T. and Hifza, R. (2005). Water Quality Report, Pakistan Council
for Research in Water Resources. Pakistan Council for Research in Water
Resources.
Cooper, P. F., Job, G. D., Green, M. B. & Shutes, R.B.E. (1996). In: Reed beds and
constructed wetlands for wastewater treatment. pp. 50-100. WRc Publications,
Medmenham, Marlow, UK.
Hammer, M. J. (2004). In: Water and wastewater technology, pp. 477-479. Prentice
hall of India, 4th edition.
IBWA. (1995). In: Plant technical manual, International bottled water association,
pp. 40-45. Revised edition.
IUCN. (2005). Drinking Water Sector Paper for ACS. IUCN-ACS Support Unit.
14
Principles and Application of Membrane Bioreactors in Water and Wastewater
Treatment.
Kargi, F. & Uygur, A. (2003). Nutrient loading rate effects on nutrient removal in a
five-step sequencing batch reactor. Process Biochem. 39, 507-512.
Khan, F. J. & Javed, Y. (2007). Delivering Access to Safe Drinking Water and
Adequate Sanitation in Pakistan. Working paper No. 21. Pakistan Institute of
Development Economics.
Landner, L. (1976). Eutrophication of Lakes, Causes Effects and Means for Control,
with Emphasis on Lake Rehabilitation, Swedish Water and Air Pollution
Research Laboratory, Stockholm, Sweden.
Lesliegrady, C. P., Glenn, T., Saigger & Henry, C. L., (1998). In: Biological
Wastewater Treatment, pp.100-159. (2nd edition) CRC Press.
Nidal, M. (2008). High strength sewage treatment in UASB reactor and an integrated
UASB- digester system. Bioresource Technol. 99 (16), 7531-7538.
Roland, L. (1997). In: Theory and practice of water and wastewater treatment. pp
660-665. John Wiley & Sons, Inc.
Saeed, M. M. & Bahzad, A. (2006). Simulation of contaminant transport to mitigate
environmental effect of wastewater in River Ravi, Pakistan J. Water Resour.
10(2), 4-52.
15
Tchobanoglous, G., Burton, F. L., Stensel, H. D. Metcalf & Eddy. (2003). In:
Wastewater engineering: treatment and reuse. pp. 350-400. International
edition. McGrawHill.
Terada, A., Hibiya, K., Nagai, J., Tsuneda, S. & Kirata, A. (2003). Nitrogen removal
characteristics and Biofilm analysis of a membrane aerated biofilm reactor
applicable to high strength nitrogenous wastewater treatment, J. Biosci.
Bioeng. 95(2), 170-178.
Vymazal, J. (2009). The use constructed wetlands with horizontal sub-surface flow
for various types of wastewater. Ecol. Eng. 35, 1-17.
Zahid, H. and Baig, M. A. (1997). Pollution of Lahore canal water in the city
premises processing of NSMTOC, 97. Article on Environmental Pollution, pp
24-26.
16
2 Chapter 2: Literature Review
Comparison of Different Treatment Options in Municipal
Wastewater Treatment
17
2.1 Characteristics of Municipal Wastewater/Domestic Wastewater
Table 2-1 Average composition of domestic sewage (Verstraete, 2004). *DW: dry weight
Gray water arises from domestic washing operation such as hand basins, kitchen
sinks and washing machines but specifically exclude foul or black water sources (toilet,
bidets and urinals) Physically, wastewater is usually characterized by a grey colour,
musty odour (Verstraete, 2004; Verstraete, 1999) and most important analysis parameters
included are ammonia, nitrate, phosphate, total and suspended solids and volatile
suspended solids (Almeida, 1999). Solids in water are 30% in suspended form and 70%
dissolved form. In wastewater treatment dissolved solids can be removed by biological
treatment and during advance treatment, membrane filtration can be used. Wastewater
18
composes of organic inorganic and various gasses which are present in dissolved form.
These organics compose of mostly grease, fat, protein, oil and pesticides or some other
components depending upon pollutant source. Domestic wastewater consists of 50% of
organic and inorganic part. Mostly wastewater contains more dissolved solid than other
solids. These dissolved solids are more difficult to remove. These dissolved solids make
part of 80-90% of inorganic components and 50-60% is organic dissolved form. Mostly
common gasses found are known as hydrogen sulfide, nitrogen, carbon dioxide and
oxygen. Hydrogen sulfide, methane and ammonia are formed due to decomposition of
organics present in wastewater (Metcalf and Eddy, 2004, Verstraete, 1999).
Wastewater contain many different type of microorganisms but the most which
are concerned in classification regarding wastewater treatment and some plants like
mosses, ferns and seed plants. Most important microbial community which likes to be
considered in treatment is protozoa, algae and bacteria. Most of pathogen enters in
wastewater from human who are suffering from different diseases or carrier of diseases.
In denitrification of these pathogens are difficult and time consuming. Coliform which is
easier to test are good indicator of presence of these pathogens but does not accurately
indicate the presence or absence of pathogen. These could be finding also in effluent
concentration of raw wastewater. Fecal coliform raw wastewater found in hundred
thousands to tens of millions in 100 ml of sample.
19
wastewater treatment plant. Wastewater in dry weather conditions consists of sanitary
wastewater. In rainy days domestic wastewater composition is changed as it diluted with
rain water and this is amplified with contaminants.
20
EE2 through filter of sand, GAC and MnO2 was 17.3%, 99% and 81% (Rudder, 2004).
This topic is getting more interest due to possible negative role of this compound
including hormonal imbalance (feminization) and altered reproductive success such as in
fish and avians (Janz, 1996; Jobling, 1998; Desbrow, 1998). It is also observed in beast,
testicular and prostate gland cancer. Moreover neurological dysfunction cases were
identified in human. These events took place at low environment concentration (Purdom,
1994; Russo, 2002). The EE2 can be tested after oxidation or anaerobic treatment and
with combination of both.
21
successfully in Europe with less maintenance. In term of settling this tank was more
efficient in dealing with larger particles than smaller particles. In this tank influent creates
recirculation eddy near the pump with generation of turbulence at the inlet and outlet weir
of the sedimentation basin which inhibit the settling. This study was proved to be an
improvement in sedimentation of larger particles (Al-Sammarraee, 2009). The efficiency
of the sedimentation tank to reduce the BOD and TSS depends on 1) eddy current of
incoming fluid 2) wind induced in open tank 3) convection heat current 4) density
gradient developed due to cold or warm water which results hindering in movement of
water from bottom to the surface (Metcalf and Eddy, 2004; Al-Sammarraee, 2009).
Generally temperature of the water under treatment is one factor which needs to be
considered during sedimentation treatment. Highest wastewater flow towards wastewater
treatment during summer and when water is cold flow reaches at its lowest. When the
temperature decreases rate of settling decreases and therefore at low temperature
detention time should be increased to allow sufficient time for settling. Sedimentation can
be speedup by the addition of coagulants/flocculants (Well, 1998). In another study,
temperature had a significant effect on cohesive settling in sedimentation basin and
settling velocity increases with temperature (stocks law), (Lau, 1994). Differences in
temperature significantly effect on mixing. It may be due to density gradient develops
stratification after change in temperature and causes poor mixing (Mehmood, 2005).
A computational fluid dynamics model was studied by Goula, to assess the effect of
influent temperature variation on solids settling in sedimentation tank. This model was
used against real sedimentation basin and then assesses the significance of influent
temperature variations. Results shows that with increase in temperature cause buoyant
plume rising which changes the direction of circular current clockwise to anticlockwise
countercurrent thus the particles remain in suspension. This led to decrease percent
removal of particle size of 250 µm from 99.5% to 76.0% during sedimentation (Goula,
2007).
22
2.3.2 Physico-chemical treatment
Domestic wastewater treatment in developing countries needs especial attention in
relation to low-cost, low energy, low maintenance and high performance systems that
contribute to environmental sustainability by producing safe and able to be used in
agriculture for crop production. Many other treatment techniques like activated sludge
systems, bio-membrane filtration are expensive to adopt in developing countries. Natural
treatment system is very good and environmental friendly but the problem is space,
constructed wetland need more space which is too expensive in the cities. Therefore a
treatment technique is desirable which should be economical and requires less space to
work efficiently. A combination of chemically enhanced primary treatment and up flow
anaerobic sludge blanket should be considered for domestic wastewater treatment as an
alternative to activated sludge system (Gautam, 2007).
Chemical treatment may be used as a pre treatment or post treatment with anaerobic
treatment in order to enhance the sedimentation and biodegradability of the domestic
wastewater. Coagulation/flocculation is commonly used process in which charge on
particles is neutralized and flocculation to describe the uniting particles into large units.
Colloidal particles that cause color and turbidity in which solid-liquid, liquid-liquid
interface play a vital role in stabilizing the colloidal impurities found in wastewater.
Colloids can also be formed from organic compounds, clay particles by soil erosion and
soap solution etc which cause turbidity in wastewater Table 2-2. These are difficult to
remove from water because it is so small to pass through filter pore and not settle by
gravitational force. Colloidal particles range up to the maximum size of 1µm.
23
Colloidal particles in wastewater can be destabilized with coagulants/flocculent
agents like alum, FeCl3 and lime by 1) reducing the repulsion forces 2) particle
destabilization which can be achieved by double layer compression, adsorption and
charge neutralization, enmeshment in a precipitate and adsorption and interparticle bridge
(Benefield, 1982). Salts of Al (III) and Fe (III) are commonly used as coagulants in water
and wastewater treatment.
24
Entrapment in a flocculent mass and iv) adsorption and inter-particle bridging. In ionic
layer compression diffuse layer of colloidal particle is compressed resulting more
opposite charge particle moving to colloidal particle making diffuse layer length. This
makes wander wall force increased and particle gets attracted. Second mechanism is
adsorption and charge neutralization. When alum in water it forms aqua metallic ion
which has high affinity with colloidal particles which results no diffuse layer left on
colloidal particle. In this way particles come together and form agglomerates. Excess
dose of alum in wastewater treatment results destabilization of particles and increase the
turbidity. Optimization of dose is very important before applying the coagulant to
wastewater treatment tank. Third step is entrapment in flocculent mass sweep coagulation
where alum is being dissociated in Al and sulphate at high dose. These coagulant form
coagulants and start moving entrapping other colloidal particles and settling down. Last is
adsorption and inter particle bridging; polymers molecules attached to colloidal particles
at one or possibly more than one sites by columbic attraction. If both have similar charge
then tail extends in to bulk of solution and attached to vacant opposite charge site. This
bridging formation result in flock formation and settle down. So coagulation is a process
involving particles destabilization followed by mixing to promote collisions between
colloidal and polymer or charge species. In this research work alum treatment was
studied and compared with other coagulants. The best coagulant alum was found
effective (p < 0.05) in COD removal of MWW. Other coagulant FeCl3 and Moringa
oleifera was not found suitable for this type of MWW containing industrial, domestic and
commercial wastewater (Kologo, 2001; Metcalf, 2004).
25
The CEPT is an interesting process, over the activated sludge treatment because
that we do not need large investment to build an entire activated sludge treatment plant.
CEPT can provide alternate sample for developing region and remote area instead of
using expensive biological treatment. It is possible to meet effluent criteria using this
method with limited technology and operational costs. CEPT does not reach the effluent
quality as activated sludge system does, but it has several advantages such as low
operating and capital cost. In activated sludge system separate treatment is required for
the nitrogen removal (nitrification and denitrification) and also requires separate
phosphorus removal steps including aerobic and anaerobic treatment (Herlman et al.,
1999). Whereas in CEPT process, phosphorus can be reduced by the addition of FeSO4
either combining with other coagulant or can be used separately in the same
sedimentation tank (Metcalf et al., 2004).
26
Table 2-3 Comparison of removal efficiencies
Natural coagulant can be used also to treat drinking water. In Zambia people are
encouraged to grow more Moringa trees to produce more natural coagulant from this tree.
This natural coagulant may be used to treat domestic wastewater at primary stage
(Nakhata, 2001).
In another study by Guida, (2007) alum optimization was tested to treat five different
MWW, i) Cuma, ii) Marcianese, iii) Nola, iv) San Giovanni, v) University pilot plant
wastewater. A series of jar test was performed with 150 and 450 mg L-1 alum dose at pH
ranging from 4 to 10 of COD varied from 330 mg L-1 to 560 mg L-1. Results show that in
Nola plant 45% of COD level was decreased but when 150 mg L-1 alum was used 79%
removal achieved. At pH 10 COD removal efficiency was decreased drastically.
Insufficient COD removal was observed in the Cuma and university pilot plant
wastewater even at an alum dose of 450 mg L-1 whereas in Nola and S. Giovanni plants
using 150 mg L-1 alum was sufficient to reduce the COD upto 160 mg L-1 and TSS 80 mg
L-1 within limits (Guida, 2007). It means wastewater characteristics important for
effective use of alum dose.
In another research work (Feo, 2008) it was studied in selection of best coagulant
to treat urban wastewater. Eight different coagulant aluminium sulfate, ecofloc 614,
ecofloc 616, ecofloc CP, ecofloc SA 7, ferric chloride, poly aluminium chloride and
sodium aluminate with dose of 10, 20 up to 50 mg L-1 was used. The cost of coagulant,
COD removal percentage and pH variation was studied. The best coagulant, Ferric
chloride, was identified for maximum 85.4% of COD removal and 7 to 20 % variation in
pH. Most expensive coagulant cost 1.6 to 1.7 euro/kg with COD removal efficiency was
less than 85.4 % of ferric chloride. In this study Aluminium sulfate was not found in good
27
percentage COD removal in urban wastewater treatment with maximum efficiency of
49.9% at dose of 50 mg L-1. Poor COD removal efficiency was observed with Ecofloc
6.2% at 50 mg L-1 while at dose of 20 mg L-1 maximum removal of 28.3% COD
indicated. Other all coagulants were observed as increasing dose with increase in COD
removal but due to cost of coagulant and effluent quality it was not feasible to exceed the
treatment dose (Feo, 2008). In that study simple criteria was used to observe the different
coagulant effects at different doses to see the effects on COD removal efficiency,
coagulant cost, sludge volume at 2 hr and pH percentage variation. In this proposed
system of chemically assisted primary sedimentation can be replaced if coagulant added
as coagulation for 5 minutes, flocculation for 5 minutes and sedimentation 120 minutes
and then discharge for secondary treatment (Feo, 2008; Harleman, 1999).
In developing countries most of the hospital waste is mixed with domestic/MWW which
can be another problem in combine treatment system because presence of antibiotics,
chemicals, dyes, reagents and drug components can harm the active microbial species
(Table 2-4). These species are involved in decomposition of organic waste in wastewater.
In the presence of pharmaceutical compounds only physico-chemical treatment can be
effective. Treatment of hospital waste mixed with domestic waste was treated with FeCl3.
Results show that coagulant dose of 175 mg L-1 was optimized where maximum COD
removal 98% was observed and no further decrease in COD with increasing dose was
observed. Filtration was followed by chemical treatment to remove suspended solids. To
disinfect the water calcium hypochlorite as disinfectant was used and observed further
decrease in COD up to 16 mg L-1 and another disinfection option is UV light treatment
for hospital waste before discharging into surface water and coastal water. This shows
physico-chemical treatment of hospital waste as best option. For the selection of best
coagulant jar test is necessary to match the coagulant with wastewater treatment for the
maximum COD removal at optimized low dose.
28
Table 2-4 Hospital wastewater comparison with urban wastewater
29
objective of this research work was to obtain a product from the CEPT sludge with high
adsorption capacity. FeCl3 was applied as the effective adsorbent for the removal of
turbidity, COD and total phosphorus. It was applied between the concentration of 0.2 to 3
g L-1. The removal efficiency was turbidity 83%, COD 48.8% and total phosphorus 89%.
It shows FeCl3 is the effective adsorbent in sludge has the role of destabilization and
condensation nuclei that ultimately help in settling the suspended particles and removal
from sludge (Xu, 2005).
30
2.10 Combine Chemical and Biological Low Cost Treatment Systems
The MWW contains 40 to 50% of COD in terms of suspended solids (Metcalf,
2004). These solids are not easily hydrolyzed in anaerobic system and continuously
feeding of such solids in wastewater increases the sludge volume. The main advantage of
anaerobic sludge blanket is to produce less sludge with better COD removal efficiency
and if sludge volume increases in short period than the COD removal efficiency
decreases. Excess sludge need to replace affecting the sludge bed (Mergaert, 1992;
Verstraete, 1999; Sayed, 1995). Natural sedimentation process can remove 40 to 50%
suspended solids before feeding to UASB reactor. Suspended solids usually take a day to
settle down to remove resistant part of the solids (Elmitwalli, 1999). To reduce the
settling time coagulant can be used to enhance the sedimentation (NDabigengesere,
1998). This step requires additional care to control the pH of influent for UASB. This
system can be more feasible where MWW blend of domestic, industries and hospital
discharge. This treatment system consists of mixing tank and same can be used for
sedimentation as well.
A study on CEPT-UASB combination by (Kologo, 1999) wastewater treatment
system consists of 20 liters working volume and UASB reactor working volume 1.2
liters. Two combinations were compared i) FeCl3 as coagulant were used in CEPT and
it’s decant was fed to UASB ii) Moringa oleifera extract were used in CEPT and it’s
decant fed to UASB Figure 2.1. Results showed that 50% COD, 75% SS and 79%
phosphate phosphorus were removed when FeCl3 were used in CEPT tank and in next
step CEPT effluent were fed to UASB with removal efficiency of COD 54%, SS 51%
and phosphate phosphorus values increased due to mineralization of the phosphorus.
UASB reactor was found successful in removal of soluble COD 55% than CEPT only
24%. Moringa oleifera was not found successful in removing Phosphate phosphorus and
COD.
31
In developing countries MWW assimilate wastewater from different sources other
than the definition of the MWW. CEPT can help to remove suspended solids and UASB
receive fewer loads, which may help to avoid recycling. In present study MWW in
Abbottabad was observed suspended solids SS >100 mg L-1 and direct fed to UASB at
HRT 12 hr was found to be successful removal of COD followed by disinfection with
waste H2O2 (40%).
Same methodology was adopted by Sunny Aiyuk using FeCl3, alum, Allied colloids
(anionic), Allied colloids Zetag (cationic), Synthofloc H-PWG (anionic), Praestol
(cationic), caldic calfloc (anionic), Betz-Benelux (cationic) and other were tested with
series of jar test to treat domestic wastewater. These tests were carried to select the best
combination of coagulant/flocculant for chemically enhanced primary treatment. The best
combination was found i) FeCl3 allied colloid E10 (anionic) ii) Alum Betez-Benelux
1558 E (cationic) decreased COD 138 and 144 mg L-1from initial 522 mg L-1of domestic
wastewater. Using selected combination of coagulants in CEPT was removed TSS 85%,
COD 73%, BOD 66%, TKN 23% and PO4-P 80% and total removal with UASB 88%,
91%, 71%, 99% and 75%. In this study effluent after UASB treatment was further
treated with zeolite to reduce ammonium to produce good quality irrigation water figure
2.2 (Aiyuk, 2004). Zeolite was effective after UASB removing 100% ammonium ions
and before UASB it was effective only 45% removal. Interstitial spaces of zeolite allow
to replace cations by ammonium through ion exchange. It was regenerated after two
when it was installed after the UASB. Higher removal efficiency was due to longer
exposure time with zeolite as UASB effluent release slowly with 0.4 g COD L-1, 10h
HRT.
Figure 2.2 Schematic of the low investment sewage treatment concept with zeolite installation
32
In another study on domestic wastewater SS 165 mg L-1, COD 320 mg L-1, TKN 33
mg L-1 and PO4-P 5 mg L-1 after days 41 to 154 removal efficiency of COD and SS were
70 and 81%. In this case no CEPT was used to remove SS and no sludge accumulation
was observed for 160 days. In this case SS was 165 mg L-1 (Kologo, 2001) where no
CEPT was found necessary but in the study by Sunny, 2004 SS more than 200 mg L-1
where CEPT was found to be necessary to improve COD removal efficiency of UASB
reactor. In Abbottabad MWW, SS was found not more than 150 mg L-1 therefore it was
not necessary to add CEPT before UASB treatment. In our results it was observed 99%
COD removal efficiency.
33
temperature 100ºC. The changes take place in its concentration during the process where
concentration increases 40% which is not allowed to use further for disinfection of
packaging material. To use 40% waste H2O2 in wastewater treatment had been studied in
this research work to find its effect on COD reduction.
34
2.11.2 Fenton reagent in AOP
In AOP Fenton reagent successfully used in wastewater and pre-treatment of
wastewater. It is consisted of ferrous salt with H2O2 in acidic conditions which allow the
production of hydroxyl radicals. It depends on temperature, H2O2 concentration and Fe2+
concentration.
These reactions have short reaction time and can be beneficial for high COD removal.
In another study of pre oxidation of an extremely polluted wastewater with the
help of Fenton’s reaction was studied by means of an experimental design, influenced by
operational parameters including temperature, ferrous ion and H2O2 concentration. The
optimal values of H2O2 and ferrous ion concentrations were 3 and 0.3 molar, respectively
and resulted in 56.4% of COD reduction. It was found that temperature indicate slight
positive change in COD removal. During first 10 minutes of Fenton reaction, COD
removal was 90% achieved. This might be very interesting to the industrialist because it
reduces COD in very short period of time. It is also considered as good pretreatment of
wastewater, where BOD is difficult (Martinez, 2003).
In another study, H2O2/UV process for the treatment of domestic wastewater was
successfully carried out. Pretreatment was studied before AOP in order to reduce the
turbidity. Alum was used between 20 – 100 mg L-1 with optimum pH results best COD
and turbidity removal at room temperature. Remaining supernatant was then treated using
H2O2/UV experiments. The results indicated that neither plain sedimentation nor
filtration showed substantial results, but alum at optimum pH of 7 and dose of 60 mg L-1
showed applicable reduction in COD 39% and turbidity 84%. This resulted in better
35
effluent COD as opposed to raw wastewater. In the next step of AOPs the rate of
hydroxyl radical generation by H2O2/UV system was studied on pH dependant and
concentration of the oxidant. Proper value of these parameters was therefore being
chosen carefully. H2O2/UV process resulted over a 95% removal for COD with no sludge
generation and high power UV lamp significantly decreases the reaction time (Yonar,
2006).
Although, rules and regulations exist but lack of implementation and absence of
proper monitoring results in problem persistence. Throughout Pakistan industrial
approach towards environment is the same. BOD levels in watercourses receiving these
wastes are as high as 800 mg L-1 and mercury levels over 5 mg L-1. Consequently,
hundreds of tons of fish are killed causing a loss of millions of rupees (CWRAS, 2005).
36
duration time of the process. Fenton’s reagents showed higher oxidation potential
compared with H2O2 and, as a consequence, better efficiency in aerobic digestion.
Fenton’s reagent also improved sedimentation properties of sludge and decreased soluble
COD. The important advantage of Fenton’s reagent application is that it may initiate the
oxidation process more effectively than H2O2. Such conclusions are based on VSS, COD
and ORP (oxidation reduction potential) analysis. The apparent disadvantage of Fenton’s
reagent application, however, is the additional formation of chemical sediment and the
fact that overdose of a reagent may cause decomposition of sludge flocs and, as
consequence, increases turbidity and some problems with sludge dewatering springs up.
When Fenton’s reagent is applied for a long time or when high doses are applied, it is
affected by colorization of liquid caused by iron salt addition (Barbusinski, 2003).
37
2.13.1 Hydrolysis
Hydrolysis is break down process of complex soluble and insoluble into smaller
molecules that can be transported into the cell and metabolize after penetration through
the cell membrane of the fermentative bacteria. Complex material converted into dissolve
material by the action of exoenzymes released by the hydrolytic fermentative bacteria.
Hydrolysis process of complex compounds is a slow process that depends on several
factors (Lettinga et al., 1996) e.g. temperature of the reactor, residence time of the
substrate in reactor, pH, substrate composition (lignin, carbohydrate, concentration of
NH4+ - N, protein and fat contents) and size of particles. Soluble product metabolize
inside the cell of fermentative bacteria converted into simpler compounds excreted by
cell. These compounds are volatile fatty acids, carbon dioxide, lactic acid, alcohols,
hydrogen, ammonia and hydrogen sulfide besides new bacterial cells. Species belong to
clostridia comprises Bacteroidaceaea, found in digestive tracts responsible to degrade
sugars and amino acids.
38
2.13.3 Methanogenesis
Formation of methane during anaerobic digestion is an end product. Acetoclastic (or
acetophilic) bacteria utilize acetic acid to convert into methane and carbon dioxide
(Droste, 2004).
CH3COOH CH4 + CO2
They use specific substrate like acetic acid, hydrogen/carbon dioxide, carbon monoxide,
methanol and formic acid. Two types of methanogenic groups involve, one use acetic
acid or methanol, other hydrogen and carbon dioxide groups named as aceticlastic and
hydrogenotrophic methanogens. Two genera involve Methanosarcina and Methanocaeta
while methanocaeta is more sensitive to pH with longer retention time and produce lower
yields of methane than Methanosarcina (anaerobic reactor) than Methanosarcins.
Methanocaeta develop filaments which is important in granule formation.
Methanosarcina are grouped together forming coccus packages and use hydrogen and
methylamine. Methane former are fastidious in their requirement of growth and
metabolism then acid former therefore methane is produced generally. Optimum pH is
7.0 and activity decreases when pH falls out of range 6.0-8.0. Due to continuous
production organic acid is responsible for environmental stress on methane formers
because methane formers fail to convert organic acids in to hydrogen.
39
production reported. Supplementation of such reactors was started to reduce the start up
period after the development of UASB.
UASB requires a special flow regime in order to provide sufficient time for
substrate to contact with sludge to assimilate. The great attraction of UASB reactor is low
sludge, maintenance, and investment. Post and pretreatment might be required for UASB
to reduce suspended solids, odor, remaining nutrients etc. This technology offers some
advantages and disadvantages. Suitable pH to run the reactor in normal mode is 6.3 to
7.8, COD between 250 mg L-1 and 400 mg L-1 an upper limit of COD is not known (Gate,
2001).
Normally influent enters into reactor from bottom and effluent exits from the top
of the reactor. Influent follows the up-flow movement contacting with sludge. Deflector
and baffle is installed in upper part of the reactor to prevent sludge discharge and upward
movement inside the reactor and it also helps sludge to sink back. Gas collector slightly
dips into water from the top of the reactor where gas accumulates and finds their path to
gas discharge and collector. Upper portion where gas is collected and effluent discharges
is called settling zone, transition zone where water separates from sludge and digestion
zone consists of sludge blanket.
Anaerobic reactor UASB is divided into four compartments: settling, gas-liquid
separator fluidized and sludge bed. Organic compounds in wastewater are hydrolyzed and
acidified by hydrolytic and acidogenic bacteria figure 2.5. The successful operation
requires a highly active biomass in the form of granules with good settling properties.
Excess sludge is periodically removed otherwise sludge bed fluidized zone decreases.
40
Table 2-5 Main advantages and disadvantages of UASB reactor
Advantages Disadvantages
Low space required Demand for know-how
Possibility to captured methane in Economically not feasible in colder
enclosed system climate at temperature lower than 15ºC
Low odour emission In complete removal of pathogens; post
Hygienic advantages treatment is required to solve this problem
Low mechanization Longer start up period to reach maximum
Low but high quality sludge production efficiency
Low demand for operational means, Lack of process knowledge
control and maintenance
Low investment and operational cost
The most of the pilot scale UASB operated at 7-19ºC and COD removal
efficiency 55-77% and hydraulic retention times of 4-72 h. Other hand full scale
installations have been reported, operating at high temperature 20-30 ºC as this
temperature is suitable for anaerobic treatment. These installations are in Sao Paulo and
Saumare in Brazil, Kanpur and Mirzapur in India, Bucaramanga and cali in Colombia.
Most of them operated at an HRT more than 4 h but never exceeded of 20 h (Kalogo,
1999).
Different polymers have been used to reduce the UASB start up period. Moringa
oleifera is a tropical plant belonging to the family Moringaceae. Water extract Moringa
oleifera seed (WEMOS) was found effective in flocculation of organic matter. Currently
it is used to treat drinking water, where it was found as good coagulating agent (Kalogo,
2001). WEMOS contained active agents are dimeric cationic proteins, molecular
weight13 kDa. The WEMOS contains several types of carbon sources e.g. carbohydrates,
lignin, lipids and other nutrients like N, P and metal ions which support microbial
growth.
41
Figure 2.3 The UASB reactor
42
Figure 2.5 Anaerobic decomposition of organic matter
43
It was observed that start-up period shortened up to 20% as compared to control
when domestic wastewater fed at COD of 320 mg L-1 and suspended solids 165 mg L-1.
There was increase in acidogenic, methanogenic and biogas production. WEMOS was
found to be effective against growth of the coccoid bacteria and growth of microbial
nuclei which was found in supporting granulation process (Kalogo*, 2001). The
experiment results of Ghangrekar, (2005) indicate that organic loading rate and sludge
loading rate between 2.0-4.5 kg COD m-3 and 0.1-0.25 kg COD kg-1 VSS d, help in
developing good characteristic sludge for the removal of organics in wastewater
(Ghangrekar, 2005). Study of physical and biological performance of UASB reactor
during its start up period, it was observed in removal 65% COD and 73% of suspended
solids. This performance was achieved in 6 weeks of operation, second period after 14
weeks expressed by biogass released. Therefore in this study process optimization
focuses on shortened start up period. Reactor showed three phases, first phase low
biochemical activity, almost no biogas production and invariability of the effluent pH. It
was confirmed by the low VSS/SS ratio observed during first 6 week. It appeared
beginning weeks of the reactor were evident in removal of COD and SS due to
interception in the reactor. It has observed by many researchers that UASB reactor can
perform good removal of COD without biogas generation (Kalogo and Verstraete, 1999).
The drop of pH, increase of volatile fatty acid and gas bubble formation are features of
acidogenic during second phase (after six weeks). Biogas produced at that time dissolved
in effluent leaving the reactor. After 22 weeks 80% total COD, 60% of soluble COD and
90% suspended solids removed, at 29C with an HRT of 4 hrs, while 68% of total COD
removed was due to an interception. Start up operation of biological reactor without
inoculation is possible and long time (14 weeks) required for effective biological
degradation (Kalogo, 2001). Presence of suspended solids in MWW negatively
influences the methanogenic activity and the chemical oxygen demand. This can be a
problem for many anaerobic wastewater treatment systems such as expanded granular
sludge bed, the up flow anaerobic sludge blanket, anaerobic hybrid reactor and hydrolysis
up-flow sludge bed. An integrated treatment concept was studied for anaerobic treatment
of domestic wastewater. In this approach continuous stir tank reactor combined with
UASB to remove settle able solids in primary sedimentation and then fed to UASB. The
44
principal advantage is to lower the negative effect of suspended solids in the UASB
reactor; producing effluent of high quality for irrigation.
45
2.13.6 Function of micro-nutrients during start-up of UASB
Role of micro-nutrients during start-up of UASB: Microbial species in UASB
reactor can be enriched with rich nutrient synthetic wastewater in order to achieve
maximum efficiency in short time period (Mahmood, 2007). Presence of macro and
micro-nutrients also help in removal of propionic acid in anaerobic digestion process.
Propionic acid is a recalcitrant which is difficult to degrade by biological means. In the
presence of supplemented macro and micro nutrients stimulate the anaerobic reactor
efficiency to remove propionic acid. A shock of high concentration of propionic acid
could harm the anaerobic species in reactor. On the contrary, gradual increase in organic
loading rate eliminates the propionic acid at high rate. Three phases of this experiment
without nutrients, with macro-nutrients and with macro & micro both nutrients; remove
3g, 18.1g and 32.8g of propionic acid. This shows that the presence of macro and micro
nutrients is clearly essential for the high removal of propionic acid during anaerobic
digestion (Ma, 2009). When a single micronutrient zero valence Fe was used, it showed
that UASB improve the removal of COD by 21% as compared to control reactor (Xu,
2005) Table 2-6.
Ammonia may cause process inhibition which is formed during the fermentation
process. This process inhibition favored by high pH. It starts formation when pH
increases above 7.5 and when its concentration increases from above 40 mg L-1 and
temperature above 30ºC. To avoid sludge bed washout from the reactor, the up-flow
velocity shouldn’t exceed from 0.2 to 1 m h-1. it can be calculated as:
V= Q/A
V= H/HRT
Higher up-flow velocity better for sludge and mixing reactor but always there is
limitation not exceeding the up-flow velocity limits. For the growth of granules up-flow
velocity is 0.25 to 0.8 m h-1.
46
Table 2-6 Function of macro and micro nutrients in anaerobic digestion
47
Table 2-7 Working goal (NEQS)
Parameters Value
HRT (Hydraulic retention time) (h) 4-20
Up-flow velocity (m h-1) 0.2-1
Charge per volume (kg COD·m-3 d-1) 0.4-3.6
Nitrogen (g L-1 ) 0.3
Phosphorus (%) 2.2 of cell volatile solids
48
sites. Compressed biogas can be used as fuel for vehicles which can be used, as same
existing technique is used for compressed natural gas. Application in vehicles requires
compression to high pressure (> 3000 psi).
49
increased upto 4.7 kg m-1·day-1the efficiency was decreased to less than 50%. This
indicates that UASB reactor was working efficiently when loading rate was 3 kg m-1·day-
1
or below. When it is more than 4kg m-1·day-1the efficiency starts to decrease. It can be
recovered by decreasing the organic loading rate below 2 kg m-1·day-1 upto 9 weeks.
DFAF was attached next to UASB so it was completely dependent upon treating
efficiency of the UASB. If the COD removal efficiency increases, loading rate decreases
for DFAF. In case when UASB is working below 50% efficiency then further combine
treatment with DFAF may attain COD removal efficiency more than 90%. This study
shows single treatment with UASB do not meet typical discharge limits and composite
system remove 99% COD 0.3 g L-1 while not yet dischargeable (Beal, 2000). Same
conclusion was made by Rafael Borja while studying treatment of palm oil mill effluent
in UASB reactor. Rate of loading was gradually increased from 16.6 g L-1 d-1 to 60 g L-1
d-1 at hydraulic retention time of 0.9 days. Results showed that 90% reduction of COD
was observed at loading rate 16.6 g L-1 d-1 and removal efficiency started decreasing till
last loading rate of 60 g L-1 d-1. This reactor acclimated as acetic acid production at the
rate of 4.1 g L-1 d-1 when loading rate of 16.6 g L-1 d-1 adjusted in a period of 100 days.
This treatment system of UASB consisted of two stages UASB. Granule formation was
observed after the 90 days in both reactors which were acclimated rapidly to the
wastewater of palm oil mill effluent and tolerant to a suspended solid concentration of 5.4
g L-1 (Borja, 1996). A study by Caixeta proved efficient treatment was observed of
wastewater from meat processing plants when operated with organic load in the range of
2.7 – 10.8 kg COD m-1 day-1removed COD 85-90% with HRTs of 22, 18 and 14 h,
respectively (Caixeta, 2002).
2.14 Conclusions
CEPT in combination with UASB were successfully used in warmer climate. But
due to high sludge production during CEPT and slow start up of UASB, it still needs
improvements. In developing countries like Pakistan cost of some coagulant some time
difficult to afford high volume wastewater treatment.
50
Advanced oxidation process can be effective in simple treatment process along with
CEPT or UASB. Newly identified compounds like ethylestrdiol can not be eliminated by
conventional treatment processes as it was observed to disrupt endocrine system.
Microbial load in effluent remains high in biological treatment system.
Oxidation of UASB effluent with chemical is an attractive integrated treatment
concept when using waste H2O2 to reduce the chemical cost. It might help in developing
countries to use one waste to treat other waste.
UASB reactor has some limitations in start up to achieve maximum efficiency in
short period of time. Still more research is required to see the effects of synthetic
nutrients to shorten the start up period. Micro nutrients are important for protein
synthesis, nucleic acid synthesis, enzymes and main attraction of using UASB in
developing countries for efficient process performance.
51
References
Almeida, M. C., Butler, D. & friedler, E. (1999). At-source domestic wastewater quality.
Urban Water. 1, 49-55.
Aiyuk, S. Amoako, J., Raskin, L., Haandel, A. V. & Verstraete, W. (2004). Removal of
carbon and nutrients from domestic wastewater using a low investment, integrated
treatment concept. Water Res. 38, 3031-3042.
Aslam, M.M., Malik, M., Baig, M.A. & Iqbal, J. (2007). Treatment performance of
compost based and gravel-based vertical flow wetlands operated identically for
refinery wastewater treatment in Pakistan. Ecol. Eng. 30, 34-42.
Benefield, L. D., Judkins, J. F. & Weand, B. L. (1982). In: Process chemistry for water
and wastewater treatment. pp. 191-210. Prentice- Hall, Englewood Cliffs, N.J.
Borja, R., Banks, C. J. & Sanchez, E. (1996). Anaerobic treatment of palm oil mill
effluent in a two-stage up-flow anaerobic sludge blanket (UASB) system. J.
Biotechnol. 45, 125-135.
Boschier, J. A. (1993). Criteria for assessing appropriate technology for sewage treatment
and disposal. Water Sci. Technol. 27 (1), 11-18.
Barbosa, A. & Sant Anna, Jr. G. L. (1989). Treatment of raw domestic sewage in an
UASB reactor. Water Res. Technol. 27, 75-82.
52
Barbusinski, K. & Filipek, K., (2003). Aerobic sludge digestion in the presence of
hydrogen peroxide and Fentons’s Reagent. Pol. J. Environ. Stud. 12, 35-40.
Bonnet, J. L., Groliere, C. A., Bohatier, J., Sargos, D., Pepin, D. & Fourneret, G. (1996).
Validation of laboratory pilot plants for wastewater treatment by natural pond
sedimentation, comparison with a reference plant. Sci. Total Environ. 193, 37-47.
http://www.worldbank.org.pk/
Desbrow, C., Routledge, E. J., Brighty, G. C., Sumpter, J. P. & waldock, M. (1998).
Identification of estrogenic chemicals in STW effluent. 1. Chemical fractionation
and in vitro biological screening. Environ. Sci. Technol. 32 (11), 1549-1558.
Droste, R. L. (2004). In: Theory and practice of water and wastewater treatment. pp.
291-308. John Wiley & Sons, Inc.
Draaijer, H., Maas Jaw, Schaapman, J. E. & Khan, A. (1992). Performmance of the
5MLD UASB reactor for sewage treatment at Kampur, India. Water Sci. Technol.
25, 123-133.
Emmanuel, E., Blanchard, J.-M., Keck, G., Perrodin, Y. (2001). Chemical, bilogical and
ecotoxicological characterisation of hospital effluents. pp. 31-33. De´ chets
Sciences et Techniques, revue francophone d’e´ cologie, industrielle, No 22–2e`
me trimestre.
53
Elmitwalli, T. A., Zandvoort, M. H., Zeeman, G., Bruning, H. & Lettinga, G. (1999).
Low temperature treatment of domestic wastewater sewage in upflow anaerobic
sludge blanket and anaerobic hybrid reactors. Water Sci. Technol. 39, 177-186.
Fan, L. Xu, N., Ke, X. & Shi, H. (2007). Numerical simulation of secondary
sedimentation tank for urban wastewater. J. Chin. Inst. Chem. Eng. 38, 425-433.
Goula, A. M., Kostoglou, M., Karapantsios, T. D. & Zouboulis, A. I. (2008). The effect
of influent temperature variations in a sedimentation tank for potable water
treatment-a computational fluid dynamics study. Water Res. 45, 3405-3414.
Grin, P. C., roersma, R. D. & Lettinga, G. (1983). Anaerobic treatment of raw sewage at
lower teremertures, In: proceedings of the European symposium on anaerobic
wastewater treatment (AWWT), ed. Van Brink, W. J. 335-347. Noordwijkerhout.
ISSN 0194-3925.
54
Gautam, A. K, Kumar, S. & Sabumon, P. C. (2007). Preliminary study of physico-
chemical treatment options for hospital wastewater. J. Environ. Manag. 83, 298-
306.
Guida, M., Mattei, M., Rocca, C. D., Melluse, G. & Meric, S. (2007). Optimization of
alum-coagulation/flocculation for COD and TSS removal from five municipal
wastewater. Desalination. 211, 113-127.
Jurgens, M. D., Holthaus, K. I. E., Johnson, A. C., Smith, J. J. L., Hethridge, M. &
Williams, R. J. (2002). The potential for estradiol and ethinylestradiol degredation
English rivers. Env. Toxicol. Chem. 21 (3), 480-488.
Jobling, S., Nolan, M., Tyler, C. R., Brighty, G. & Sumpter, J. P. (1998). Widespread
sexual disruption in wild fish. Env. Sci. Technol. 32 (17), 2498-2506.
55
Korner, W., Bolz, U., Submith, W., Hiller, G., Schuller, W., Hanf, V. & Hagenmaier, H.
(2000). Input/output balance of estrogenic active compounds in a major municipal
sewage plant in Germany. Chemosphere. 40, 1131-1142.
Kalogo, Y., M’Bassiguie Seka, A. & Verstraete, W. (2001). Enhancing the start-up of a
UASB reactor treating domestic wastewater by adding a water extract of
Moringa oleifera seeds. Appl. Microbiol. Biot. 55, 644-651.
Kalogo, Y. & Verstraete, W. (1999). Development of anaerobic sludge bed (ASB) reactor
technologies for domestic wastewater treatment: motives and perspectives. J.
Micro. Biotechnol. 15, 523-534.
Lange, R., Hutchinson, T. H., Croudace, C. P., Siegmund, F., Schwein, H., Hampe, P.,
Panter, G. H. & Sumpter, J. P. (2001). Effects of the synthetic estrogen 17 ά
Ethinylestradiol on the life-cycle of the fathead minnow (pimephales promelas).
Env. Toxicol. Chem. 20 (6), 1216-1227.
Lettinga, G., Van Velsen, A. F. M., Hobma, S. W., De Zeeuw, W. & Klapwijk, A.
(1980). Use of the upflow sludge blanket (UASB) reactor concept for biological
wastewater treatment, especially for anaerobic treatment. Biotechnol. Bioeng. 22,
699-734.
56
Lettinga, G. De Man, A. Vanderlast, A. R. M. Wiegant, W. Van Knippenber, K. Frijns, J.
& Van Buuren, J. C. L. (1993). Anaerobic treatment of domestic sewage and
wastewater. Water Sci. Technol. 27, 67-73.
Lettinga, G., Roersma, R. & Grin, P. (1983). Anaerobic treatment of raw domestic
sewage at ambient temperature using a granular bed UASB reactor. Biotechnol.
Bioeng. 25, 1701-1723.
Ma, J., Mungoni, L. J., Verstraete, W. & Carballa, M. (2009). Maximum removal rate of
propionic acid as a sole carbon source in UASB reactors and the importance of
the macro- and micro nutrients stimulation. Bioresource Technol. 100, 3477-
3482.
Metcalf and Eddy. (2004). In: Wastewater engineering, treatment disposal reuse. pp.
1334-1338. Mc Graw-Hill, Inc, New York.
57
NDabigengesere, A. and Narasiah, K. S. (1998). Use of Moringa oleifera seeds as a
primary coagulant in wastewater treatment. Env. Technol. 19, 789-800.
Purdom, C. E., Hardiman, P. A., Bye, V. V. J., Eno, N. C., Tyler, C. R. & Sumpter, J. P.
(1994). Estrogenic effects of effluents from sewage treatment works. Chem. Ecol.
8(4), 275-285.
Rudder, D. D., Wiele, T. V., Dhooge, W., Comhaire, F. & Verstraete, W. (2004).
Advanced water treatment with manganese oxide for the removal of 17 ά-
ethynylestradiol. Water Res. 38 (1), 184-192.
Singh, R. P., Kumar, S. & Ojha, C. S. P. (1999). Nutrient requirement for UASB process:
a review. Biochem. Eng. J. 3, 35-54.
Snyder, S. A., Keith, T. L., Verbrugge, D. A., snyder, E. M., Gross, t. S., Kannan, K. &
Giesy, J. P. (1999). Analytical methods for detection of selected estrogenic
compounds in aqueous mixtures. Environ. Sci. Technol. 33 (16), 2814-2820.
Schellinkhou, A. Osorio, E. (1994). Long term experience with the UASB technology for
sewage treatment on large scale, In: Proceedings of the international symposium
on anaerobic digestion. RSA Litho, Cape Town, 251-252.
58
Sayed, S. K. I. A. & Fergala, M. A. A. (1995). Two stage UASB concept for treatment of
domestic sewage including sludge stabilization processes. Water Sci. Technol. 32,
55-63.
Stoll, U. (1996). Liquid effluent treatment sewage sludge management and industrial
effluent standards. Resour. Conc. Recycle.16, 113-133.
http://www.h2o2.com/intro/properties.html.
Wang, D., Shin, J. Y., Cheney, M. A., Spostito, g. & Spiro, T. G. (1999). Manganese
dioxide as a catalyst for oxygen independent atrazine dealkylation Env. Sci.
Technol. 33(18), 3160-3165.
Xu, G. R., Zhang, W. T. & Li, G. B. (2005). Adsorbent obtained from CEPT sludge in
wastewater chemically enhanced treatment. Water Res. 39, 5175-5185.
Yin, K, 2009, Ratio of nitrogen to phosphorus in the Pearl River and effects in the
estuarine coastal water: nutrient management strategy in Hong Kong. Phys.
Chem. Earth, Accepted manuscript.
59
Zeng, Y., Yang, C. Zhang, J. & Pu, W. (2008). Feasibility investigation of oily
wastewater treatment by combination of zinc and PAM in
coagulation/flocculation. J. Hazard. Mater. 147, 991-996.
60
3 Chapter 3:
Municipal Wastewater Treatment by Coagulation
61
Abstract
Three coagulants viz. alum, FeCl3 and Moringa oleifera seed extract were
compared for treating MWW. The wastewater samples were collected from a drain near
the Murree Road in Abbottabad city. The initial treatment depicted that alum was a
suitable coagulant, while the other two caused color development and increased COD in
the effluent. Subsequently, wastewater samples were treated with graded concentrations
(4~32 mg L-1) of alum in batch series, and shacked at 600-620 rpm for five minutes. The
treated samples were analyzed for various water quality parameters to examine the
effective coagulation and flocculation process in the wastewater. There was an increase
in TDS and electrical conductivity with the increasing levels of alum above the optimized
values (22 to 30 mg L-1). The proposed primary treatment strategy of wastewater
treatment with alum is suitable for reducing the pollutants load in the sewer system.
Key words; Chemical oxygen demand, Total dissolved solids, Total suspended solids,
Total Kjeldahl nitrogen
62
3.1 Introduction
Wastewater generally contains a wide variety of colloidal impurities, which are
not settled by gravitation in natural sedimentation process and can pass through the pores
of most common filtration media. These colloidal particles are present in wastewater in
well-stabilized form. The removal of colloids and suspended solids (SS) from wastewater
needs destruction of the stabilizing forces leading to coagulation. Destabilization can be
achieved by double layer compression, adsorption and charge neutralization, enmeshment
in a precipitate and adsorption and inter-particle bridging (Benefield, 1984). Municipal
wastewater contains SS and TDS, which increase the COD and reduce the DO
concentration. Primary treatment is the first stage of wastewater treatment that removes
floating solids, and generally removes 50-70% of the SS and 40-50% of the associated
COD in the wastewater.
Natural sedimentation takes longer time to remove a part of the resistant fraction
of the SS. Synthetic coagulants are efficient for SS and COD removal from domestic
wastewater within reasonably short time (Kologo, 1999). Sedimentation is high when
particle size is greater than 50 µm and lesser below 2 µm size (Benefield, 1984;
Tchobanoglous, 2003). For low strength wastewater (COD < 500 mg L-1) alum treatment
can also be important in the removal of SS and TDS.
The treatment infrastructure can be smaller for CEPT, which reduces capital
costs. The present research work was undertaken to test various coagulants such as Al2
(SO4)3, FeCl3, and Moringa oleifera seed extract to settle down the organic matter and to
63
optimize the concentration of a suitable coagulant for the efficient removal of settleable
solids and colloidal particles in the MWW.
64
3.2 Materials and Methods
3.2.1 Collection of MWW
The MWW samples were collected fortnightly from the open flowing stream of
MWW near the Murree Road in Abbottabad city (Figure 3.1) during February 2007 to
February 2008 between 10:00 a.m. to 12:00 noon. These samples were brought to the
laboratory within 30 minutes and stored for subsequent experiments. This MWW also
contains small quantities of industrial wastewaters originating from small industrial areas
of Abbottabad.
Figure 3.3 shows the concentrations of COD after alum treatment in different samples.
Seven samples collected at various intervals were run to see the effectiveness of alum for
the COD removal. Decrease of COD level in treated wastewater continued until the last
dose of 32 mg L-1 was applied. It was observed that alum dose and COD removal
efficiency had a linear relation.
With the increasing alum doses, TDS also increased. One of our objectives was to
find optimum alum dose where no increase in TDS could happen. Figure 3.5 shows that
there was no increase in TDS up to alum dose of 30 mg L-1; however, at 50 mg L-1 of
67
alum dose TDS started to increase again. It was also observed that cleaner decant formed
at higher doses of alum. The increase in TDS may cause hydrolysis of alum forming
strong acids, which enhance the ionic strength of the medium (results not shown).
Therefore, we limited the dose between 20 and 30 mg L-1.
68
sedimentation, not much decrease in TSS was observed and at 32 mg L-1 52% removal of
TSS was observed.
The TSS removal was also significantly (p < 0.05) affected by the addition of
alum which showed promising results where the TSS removal of 67% was achieved.
Most of the samples contained TSS > 100 mg L-1. Natural sedimentation lasts for 6 hours
or even more to settle down the suspended solids. The settling of suspended solids can be
effectively enhanced by alum addition. Suspended solids removal is important before
secondary treatment. It is evident in Figure 3.6 that the alum addition of 20 mg L-1 of
alum dose was not much effective and enough to decrease the suspended solids load. The
alum treatment resulted in the highest removal of 70% TSS (Figure 3.5).
The allowable TSS limit in the effluent is 35 mg L-1 (Harleman, 2001). During the
coagulation and flocculation process, some part of the dissolved solids also settles down
under the large flock settling. The advantage of alum treatment is that it produces less
sludge than other coagulant like lime. When alum is added to wastewater, the following
reaction takes place (Tchobanoglous, 2003, Guida, 2007):
69
Al2 (SO4)3·18H2O +3Ca(HCO3)2 3CaSO4+2Al(OH)3+6CO2+18H2O
The insoluble aluminum hydroxide is a gelatinous flock that settles down, sweeping out
the suspended material (Kim, 2008).
Figure3.6 Effect of different concentrations of alum on removal percentage of TSS from MWW
70
can be an effective way to reduce the chances of eutrophication. For the phosphorus
reduction, alkalinity, pH, quantity and nature of suspended solids are the important
factors that may be considered during wastewater treatment. The desired pH is 6 to 7.5
along with sufficient alum dose for obtaining the optimum results. Sarkar, 2006; Pinotti,
2001; Aiyuk et al., 2004 demonstrated that the maximum removal of total phosphorus
occurred at pH 8.
Figure 3.7 Effect of different concentrations of alum on removal percentage of TSS from MWW
We observed that optimized alum dose was not sufficient for the removal of
ortho-P to meet the NEQS (Figure 2.7; Chapter 2). Increase in alum dose to reduce the
ortho-P resulted in an increase of the effluent’s TDS. Eutrophication may start at 1 mg L-1
of available phosphorus. Nitrogen to phosphorus ratio of 10-16:1 is ideal for
eutrophication (Zheng, 2004). Our main target was to reduce the COD up-to acceptable
level. It is suggested that secondary treatment is required in order to reduce Ortho-P
concentrations in the treated effluents. Addition of 24 mg L-1 alum did not significantly
(p > 0.05) remove TK-N. The highest TK-N removal rate was observed during initial
alum treatment and at higher alum doses removal rate was not significant (Figure 3.8).
71
Figure 3.8 Effect of different concentrations of alum on removal percentage of total kjeldahl nitrogen
of MWW
Figure 3.9 Effect of different concentrations of alum on the removal of turbidity in MWW
72
treatment undergo a series of hydrolysis processes producing charged species which
interact with negatively charged colloidal particles causing them to destabilize. These
destabilized particles form flocks or bridges reducing the turbidity of wastewater by
settling down. The NEQS for acceptable turbidity is >5 NTU. The highest turbidity
reduction was observed when 32 mg L-1 alum level was used (Figure 3.9).
3.5 Conclusions
Effects of various coagulants viz. FeCl3, Moringa oleifera seed extract and alum
were studied for their suitability to treat MWW. Different concentrations (4~32 mg L-1)
were applied in a series of batch mode at 600-620 rpm stirring for five minutes. There
was an increase of TDS when the level of alum was increased above the optimized value
of 32 mg L-1. The highest rate of pollutants removal load was observed when 22 to 32 mg
L-1 of alum was used. Therefore, alum concentration in the range of 22 to 32 mg L-1 was
an optimum dose for MWW treatment.
73
Table 3-1 The economic analysis of various treatment options for MWW
74
References
Aiyuk, S., Amoako, J., Raskin, L., Haandel, A. V. & Verstraete, W. (2004). Removal of
carbon and nutrients from domestic wastewater using a low investment, integrated
treatment concept. Water Res. 38, 3031-3042.
APHA, American Public Health Association. (2005). Standard methods for the
examination of water and wastewater (21st Edition), American Public Health
Association, Inc., New York USA.
Benefield, L. D. Judkins J. F. & Weand, B. L. (1984). Process chemistry for water and
wastewater treatment. pp 193-199. Prentice-Hall, Inc., Englewood Cliffs, New
Jersey.
Guida, M., Mattei, M., Rocca, C. D., Malluso, G & Meric, S. (2007), Optimization of
alum-coagulation/flocculation for COD and TSS removal from five municipal
wastewater. Desalination. 211, 113-127.
Heinzman, B. (1994). Coagulation and flocculation of storm water from a separate swer
system- a new possibility for enhanced treatment. Water Sci. Technol. 29 (12),
267-278.
Joaquin, R. & Teresa, G. (2007). Aluminium sulfate as coagulant for highly polluted cork
processing wastewaters: removal organic matter. J. Hazard. Mater. 148, 15-21.
Kalogo, Y., Séka, A. M. & Verstraete, W. (2001). Enhancing the start-up of a UASB
reactor treating domestic wastewater by adding a water extract of Moringa
oleifera seeds. Appl. Microbiol. Biotechnol. 55, 644-651.
75
Kologo, Y. & Verstraete, W. (1999). Technical feasibility of the treatment of domestic
wastewater by a CEPS-UASB system. Env. Technol. 21, 55-65.
Tchobanoglous, G., Burton, F. L., Stensel, H. D., Metcalf & Eddy. (2003). In:
Wastewater Engineering: treatment and reuse. pp. 361-411. International Edition.
McGrawHill.
Xu, G. R., Zhang, W. T. & Li, G. B. (2005). CEPT an innovative approach to urban
wastewater treatment in the developing world. Water Rres. 39. 5175 – 5185.
Zheng, P., Xu, X. Y. & Hu, B. L. (2004). New theory and technology for biological
nitrogen removal. Science Press, Beijing.
76
4 Chapter 4:
Municipal Wastewater Treatment by Waste Hydrogen Peroxide
77
Abstract
Wastewater treatment is a challenging task in order to meet the demands of ever-
increasing human population and industrial development. AOPs show promising results
if applied to wastewater treatment. Waste H2O2 (40%) collected from a food industry
after tetra pack disinfection was employed in batch experiments to oxidize MWW.
Various H2O2 doses (1, 1.5, 2 and 2.5 ml L-1) were applied to evaluate its influence on
COD, BOD5, pH, turbidity and fecal coliforms. With the increasing H2O2 concentration,
BOD5 and COD significantly (p< 0.05) reduced to70 and 93 mg L-1, respectively, along
with 51.72% reduction of turbidity at 2.5 ml L-1 of H2O2 thus meeting the NEQS. No
significant change in pH was observed during the application of 40% waste H2O2 which
fluctuated in the range of 8.31-8.46.
78
4.1 Introduction
Fresh and pure water is one of the basic necessities of growing world population
on earth. Pakistan mostly located in arid to semi-arid region with scarce water supplies
thus needs to collect and treat the wastewater (World Bank, 2008). Available water
resources are continuously depleting with constantly increasing discharge of wastewater,
thus, recycling MWW can be an effective choice for coping with water shortage. The
amount of discharged wastewater has profound effect on the environmental quality,
especially on water bodies and prospects of future generations. Hence, sustainable use of
available water will not only minimize adverse environmental impacts but also avoid
depletion of available pure water resources.
Wastewater treatment is a challenging task in order to meet the demands of ever-
increasing human population, sustainable agriculture and industrial development. For
wastewater, several treatments options exist, whose application depends on specific
objectives of cleaned wastewater reuse (Geissen, 2000). For wastewater treatment,
advance processes like chlorination and ozonation are compact and guarantee a better
quality of water produced (Bull, 1990; Ksibi, 2006) but they are expensive.
In AOPs; oxidation potential of hydroxyl group, of very reactive and short-lived
oxidants is utilized. Use of H2O2 is one of the AOPs techniques used alone (De Morais,
2005; Ksibi, 2006) or with some catalyst i.e., iron (Glaze, 1987), or UV light (Lazarova
et al., 2000; Liotta, 2009; Fernando, 1997) or O3 (Millero, 1989), which result in
reduction of BOD and COD of wastewater. Thus, current research was conducted, as an
attempt, to check the effectiveness of H2O2, as a strong oxidizing agent, in overall
reduction of organic load of MWW of Shaikhulbandi, Abbottabad, Pakistan.
H2O2 is used in many industries to disinfect the packaging material (Olmez,
2009). Use of H2O2, in tetra pack aseptic packaging of juices and milk, is important to
disinfect the packaging material Tetra Brik Aseptic (TBA) machine. Use of 37% H2O2 is
recommended for disinfection purpose. After production period of 100 hours, the
concentration of H2O2 is increased upto 40% which is not reused in TBA machine and is
drained into water bodies.
79
Statistics revealed that the cost of chemical treatment of domestic or MWW is
quite expensive (Song, 1992); however, such treatment is very efficient and time saving.
The addition of H2O2 to treat domestic wastewater has been demonstrated previously
(Ksibi, 2006); however, the use of fresh H2O2 can be very costly. It was hypothesized that
waste H2O2 generated from food industry in Pakistan could be employed to treat
domestic wastewater which might be a cost efficient and quite feasible idea.
The specific objective of the present research was to explore the effectiveness of
used H2O2 40% to reduce the BOD and COD of MWW.
Parameter Value
pH 8.14
-1
BOD (mg L ) 202
-1
COD (mg L ) 327
BOD/COD 0.62
80
40% H2O2 for BOD, COD removal and fecal coliform reduction, a series of experiments
were conducted with various H2O2 concentrations i.e., 1, 1.5, 2 and 2.5 ml L-1. In these
experiments, BOD and COD were measured throughout the reaction period of 0, 30, 60,
90, and 120 min.
81
manual by using hydrometer and temperature. The H2O2 value was obtained after
connecting temperature and hydrometer reading on third scale of H2O2 W/W (Tetra Pak,
2008).
Treatment of 1 ml L-1 used 40% H2O2 reduced BOD by 10 mg L-1, in first 30 min.
The highest decrease to 60 mg L-1 BOD was observed after 120 min of application of 2.5
82
ml L-1 H2O2. By increasing the concentration of used 40% H2O2 to 1.5, 2 and 2.5 ml L-1,
BOD values were reduced at a very rapid rate in first 30 min The maximum BOD
reduction was observed at highest concentration of used H2O2 treatment, in first 30
minutes and later BOD reduction rate was slower. Perhaps most of the reaction occurred
in the first phase, mixing and homogenization resulted in complete H2O2 consumption in
120 minutes (Figure 4.1). Percentage reduction of BOD was highest at 2.5 ml L-1 H2O2
i.e. 70% and was least at 1 ml L-1 after 120 minutes.
83
after 2hrs. By increasing the dose of 40% H2O2 from 1 to 1.5, 2 and 2.5 ml L-1, COD
values, reduced rapidly in first 30 min; however, subsequent COD reduction was at a
slow rate in next 2 hrs, revealing that mixing and homogenization may have affected
COD reduction in comparison to BOD5 of MWW. The COD values decreased with the
increasing dose of 40% H2O2 and reached to 93 mg L-1 after 2 h of treatment, which
satisfied the NEQS. Thus, the use of H2O2 only is particularly efficient for COD removal
in this case. These results prove the degrading action of the waste H2O2 for the organic
matter of the wastewater. Based on these results, we achieved the purification of the
MWW by the waste H2O2.
84
ratio to 0.8 after 30 minutes of H2O2 application then it stabilized around 0.7. Therefore,
the biodegradability of domestic wastewater was improved greatly. Lower amounts of
H2O2 caused lowering of BOD5/COD ratio as illustrated in Figure 4.3. The active forms
of oxidants are released from H2O2 in the form of OH- and HO2- produced resulting
increase in BOD5/COD ratio (Metcalf & Eddy, 2003; Ksibi, 2006).
For MWW treatment the effect of three coagulants viz. alum, FeCl3 and Moringa
oleifera seed extract were investigated. The wastewater samples were taken from the
Abbottabad city drain near Murree road. the first treatment illustrate that alum was most
appropriate coagulant, while the other two produced color and also increased the COD of
the effluent. Finally, in the batch series wastewater samples were treated with graded
-1
concentrations (4~32 mg L ) of alum. To determine the effective coagulation and
flocculation process in the wastewater, the treated samples were investigate for various
water quality parameters. TDS and electrical conductivity were increased with the
increasing levels of alum above the optimum values (22 to 30 mg L -1 (IHP, 2008; Song,
1992; Ksibi, 2006).
85
4.3.4 Turbidity removal
In the Figure 4.4. the effect of various concentrations of H2O2 treatment on
turbidity was observed after oxidation of organic matter. H2O2 is a week acid and has
strong oxidizing properties and is therefore a powerful bleaching agent. The rate of
decomposition is dependent on the temperature and concentration of H2O2. Using 1 ml L1
H2O2 treatment caused 74.13% reduction in turbidity with 43 naphelometric turbidity
units (NTU). At 1.5 ml H2O2 per liter, 67.24% turbidity was reduced and only 51.72%
(26 NTU) reduction was observed at 2 ml of H2O2. A sharp slope in Figure 4.4 shows
that the maximum effective dose in reducing turbidity was 2.5 ml L-1. Turbidity
decreased with decrease in COD indicating that oxidation of organics took place in
wastewater.
pH
Table 4-2 The economic analysis of various treatment options for MWW
87
4.3.5 Effect on pH after addition of H2O2
The changes of pH after the addition of 40% waste H2O2 have been illustrated in
Figure 4.5. No significant change in pH was observed after dosing with 1 ml L-1 40%
H2O2 and during first 30 minutes pH was increased from 8.14 to 8.17 and reached upto
8.31 in 2 hrs. But at 1.5 ml L-1, pH increased, from 8.14 to 8.37 in 2 hrs. Similarly, doses
of 2 and 2.5 ml L-1 caused an increase in pH from 8.42-8.46. Increase in pH, at different
doses of 40% H2O2 might be due to oxidation by H2O2, which resulted in release of some
bases.
4.4 Conclusions
Waste H2O2 used 40%, proved as powerful oxidant, in minimizing the organic
load of MWW. The optimum dose of waste H2O2 was found as 2.5 ml L-1 which
significantly (p< 0.05) reduced BOD5 and COD in 120 min, thus meeting the NEQS for
MWW. The results revealed that disinfection capacity of 40% waste H2O2 at application
rate 2.5 ml L-1 caused significant reduction of fecal coliform populations to less than half
of the initial value while treating MWW.
88
References
APHA, American Public Health Association, Inc. (2005). Standard methods for the
examination of water and wastewater (21st Ed.), New York, USA.
George, T. (2004). In: Wastewater engineering treatment and reuse. pp. 1196-1200. 4th
edition.
Glaze, W.H. (1987). The chemistry of water treatment processes involving ozone,
hydrogen peroxide, and ultraviolet radiation. Ozone-Sci. Eng. 9, 335-342. Online:
Accessed date 17/10/2008.
http://www.scribd.com/doc/7164171/DK2874CH1.
Ksibi, M. (2006). Chemical oxidation with hydrogen peroxide for domestic wastewater
treatment, Tunisia. Chem. Eng. J. 119, 161–165.
Lazarova, V., Cirelli, G., Jeffrey, P., Salgot, M., Icekson, N. & Brissaud, F. (2000).
Enhancement of integrated water management and water reuse in Europe and the
Middle East. Water Sci. Technol. 42, 193–202.
Liotta, L. F., Gruttadauria, M., Di Carlo, G., Perrini, G. & Librando, V. (2009).
Heterogeneous catalytic degradation of phenolic substrates: Catalysts activity. J.
Hazard. Mate. 162, 588-606.
89
Metcalf & Eddy. (2003). In: Wastewater engineering treatment and reuse. pp. 1196-
1202. McGraw-Hill.
Millero, F.J., LeFerriere, A., Fernandez, M., Hubinger, S. & Hershey, J.P. (1989).
Oxidation of H2S with H2O2 in natural waters. Env. Sci. Technol. 23, 209–213.
Song, N.T., & Hiraoka, M. (1992). Anaerobic treatment of sewage sludge treated by
catalytic wet air oxidation process in up flow anaerobic sludge blanket reactors.
Water Sci. Technol. 26, 867–895.
Tetra Pak Technical data manual. (2008). Hydrogen peroxide, Doc. No.OM-2771726-
0101 pp 8-9.
Verstrate, W. (1998). In: Microbial ecology. Practical course notes, Ghent University
Belgium.
90
5 Chapter 5:
Integrated Carwash Wastewater Treatment by Hydrogen
Peroxide
91
Abstract
Car wash wastewater (CWW) contains petroleum, hydrofluoric acid, ammonium
bifluoride products, paint residues, rubber, phosphates, oil, grease and volatile organic
compounds (VOC’s). The present study dealt with various investigations conducted for
the treatment of CWW. A treatment system of five liters capacity was designed in the
laboratory. Due to high load of oil and grease, CWW was aerated and scum was
removed. Alum was used as coagulant in primary treatment which resulted 93% and 97
% reduction in COD and turbidity. During secondary treatment CWW was further treated
with waste H2O2 which resulted in further 71% and 83% reduction in COD and turbidity,
respectively. Other desirable changes were also observed in pH, TDS, conductivity and
DO contents. It was concluded that designed system could be effectively used to treat
carwash wastewater that could be reused in the same station.
Keywords: Car wash wastewater, coagulation, waste H2O2, chemical oxygen demand,
turbidity
92
5.1 Introduction
Water is one of the most precious needs for life on earth. Scarcity of water can be
handled if proper planning is set for wastewater treatment, reuse or discharge into aquatic
system. In developed countries, carwash industry is conscious of the needs for recycling.
Developing courtiers are still behind to develop conscious for their wastewater produced
by carwash industries. Cars that are washed in the street can pollute streams, rivers, bays
and estuaries (Huybrechts et al., 2002). The soaps, oil and grimes that run off the car into
the gutters, go into the storm water system. Storm water unlike the water that enters the
sewers does not undergo treatment before it is discharged into waterways. Any pollutants
in storm water end up in our lakes, rivers, harbors and oceans, and are considered non-
point source pollution (EPA, 1994).
Wastewater from car washing stations contains a number of impurities such as
sand and dust, free oil, grease, oil/water emulsion, carbon, asphalt, salts, surfactants and
organic matter, which is discharged directly into municipal sewage treatment plant
(Hamada and Miyazaki, 2004). A non the average, 100 liters water is generated per car
and at least 10 m3 of water is discharged from a car wash station per day, there is still a
large amount of water consumed in city. Due to the amount of the water and complexity
of the water quality, from a viewpoint of environmental protection and effective
utilization of water resources, reuse of carwash water is an important subject.
Furthermore, a small space and high efficient treatments are required due to the limited
space of car wash station and high reuse water quality for car washing.
The wastewater generated from the carwash is discharged into the sewage system
without any treatment. The treatment of such wastewater needs diverse methods, which
can be economical as well as effective. A cellulose acetate hollow fiber type ultra
filtration membrane was used to enhance the process for the treatment and reuse of the
wastewater (Toyozo and Miyazaki, 2004). A carwash recycling and reuse system was
also designed by Al-Odwani et al., (2007). In another study nanofilteration retaining
surfactants were used to reduce organic components (Boussu et al., 2006).
93
The aim of this study was to explore the possibility of integrated treatment concept
for carwash wastewater to an acceptable level so that it can be discharged into water
bodies.
Table 5-1 Characteristics of the raw car wash wastewater
Parameters Characteristics
pH 8.75±0.05
Conductivity (µS/cm) 1289.6±0.577
TDS ( mg L-1) 644.33±0.55
TS ( mg L-1) 5855.66±10
Salt (%) 2.5±0.01
DO ( mg L-1) Nil to 0.90±0.002
Turbidity (NTU) 772±1
COD ( mg L-1) 1019±2
Oil contents ( mg L-1) 83.7±0.3
Aeration tank was linked with second tank containing a mixing apparatus with a
rotation speed set at 480-500 rpm. In mixing chamber alum was added and mixed. The
tanks were made up of glass-fiber material with capacity of 1.5 liters each. For chemical
treatment, Al2(SO4)3.16H2O was used and optimized by using concentration of 10, 20 mg
L-1 to 80 mg L-1, after the removal of oil. Last tank was used to mix waste H2O2 (40%)
94
with the optimized dose of 2.5-3 ml L-1. The experiments for wastewater treatment were
carried out at the ambient temperature (25oC).
95
Figure 5.2 Effect of aeration on oil contents of CWW
96
5.3.2 Effects of treatment on turbidity of CWW
The wastewater generated after car washing contains detergents, shampoo and diesel,
the materials which make the carwash wastewater very turbid. The present treatment
strategy resulted in reducing turbidity from 772 NTU to 33 NTU, showing a 96%
reduction when 80 mg L-1 of alum was added (Figure 5.3). From initial turbidity value of
772 NTU an alum dose of 10 mg L-1 caused turbidity reduction to 289 NTU. Increasing
alum dose to 20 mg L-1 and 30 mg L-1 showed no appreciable decrease in turbidity
(62.85% and 66.58%, respectively). During coagulation, suspended particles are
destabilized to promote their agglomeration producing larger particles that can be readily
removed during subsequent treatment processes. In many cases, dissolved organic
substances may be absorbed on the surface of suspended solids particles and are
therefore, removed as well. Colloidal size particles typically carry an electrical charge
(Metcalf and Eddy, 2003). When used at relatively low doses (< 5 mg L-1), charge
neutralization (destabilization) is believed to be the primary mechanism involved. At
higher dosages, the primary coagulation mechanism is entrapment.
97
Figure 5.4 COD Reduction (mg L-1) of CWW at different application rates of alum
98
5.3.5 Effect of treatment on pH of CWW
The pH of the treated wastewater decreased after the addition of alum and it
increased again when H2O2 was added in CWW. Optimum particle removal by sweep
flock occurs in the pH range of 7 to 8 with alum (Metcalf and Eddy, 2003). The CWW
was treated with optimized dose of 80 mg L-1 of alum with COD removal 82.33% where
post treatment pH observe was 7.2
99
. The combination of alum prior to waste H2O2 addition seemed quite feasible as
alum addition caused pH decrease around 7.5 and it increased again when H2O2 was
added. Treatment combination was found very effective in COD reduction; color
removal, odor and pH control (Figure 5.6).
100
Figure 5.8 Removal percentage of TDS, COD, Turbidity and Oil contents from CWW
In the present age of water crisis, it is highly desirable to treat and conserve large
amounts of wastewaters generated from carwash industry that can be reused in same
industry or in agriculture. To address this problem various reuse systems for carwash
water such as sand filtration (Nakajima et al, 1986), absorption (Okumura and Onoue,
1978), ozone (Camilo et al.,1999) and biological (Suzuki et al., 2000) treatments have
been previously developed and commercialized. Nevertheless, most of these systems are
not satisfactory for the quality of reuse water, especially because of the difficulty in
perfect removal of both particles and oil-water emulsion (Hamada and Miyazaki, 2004).
A small space and low-cost treatments are required for the reuse of carwash water
(Hamada and Miyazaki, 2004). Pretreatment using a conventional flocculating agent
before the membrane system has been well known as a technique to remove fouling
substances and make permeation flux increase (Harris et al., 1976; Lahoussine-Turcaud
et al., 1990a; Lahoussine-Turcaud et al., 1990b; Winfield, 1976). If this technique is
directly applied to the reuse of carwash water, a large space, pH control and large amount
of several kinds of flocculating agents are necessary because it is difficult to remove the
oil-water emulsion completely that is in carwash wastewater (Hamada and Miyazaki,
2004).
101
Table 5-2 Characteristics of the car wash wastewater before and after the treatment. *Below
Detection Limit
The uniqueness of the present study was that we applied aeration initially that
effectively removed more than 95% oil content from CWW. Aeration was followed by
alum addition as a coagulant. Finally, waste H2O2 was applied to oxidize most of COD
from CWW. The effect of treatment strategy on the characteristics of CWW has been
shown in Table 5-2. It is evident that the present approach is cost effective and requires
less space without any pH control. However, little concern is the hardness of treated
wastewater which needs some treatment before it can be reused.
5.4 Conclusions
The integrated treatment processes for CWW consisting of aeration, alum and
waste H2O2 reduced the 96% of the oil contents from carwash wastewater. Other
parameters like COD, turbidity and TDS were reduced upto 93%, 94% and 74%,
respectively. The present approach is cost effective and requires less space without any
pH control. Thus the treatment process can be applied on pilot scale to further evalute its
efficiency.
102
References
Al-Odwani, A., Ahmed, M. & Bou-Hamad, S. (2007). Carwash water reclamation in
Kuwait. Desalination. 206, 17-28.
APHA, American Public Health Association, Inc. (2005) Standard methods for the
examination of water and wastewater (21st Ed.), New York, USA.
Baisali, S., Chakrabarti, P. P., Vijaykumar, A. & Kale, V. (2005). Wastewater treatment
in dairy industries- possibility of reuse. Desalination. 195, 141-152.
Bhatti, Z. A., Mahmood, Q., Raja, I. A., 2009. Sewage water pollutants removal
efficiency correlates to the concentration gradient of amendments. J. Chem. Soc.
Pakistan. 31, 665-673.
Boussu, K., Kindts, C., Vandecasteels, C. & Van der Bruggen, B. (2006). Applicability of
nanofiltration in the carwash industry. Sep. Purif. Technol. 54, 139-146.
Camilo, V., Gonzalo, A. & Kirby, M. (1999). A new high efficiency automatic car wash
water recycling system. In: WEF/Purdue Industrial Wastes Conference,
Indianapolis, USA. 938-954.
Hamada, T., Miyazaki, Y., (2004). Reuse of carwash water with a cellulose acetate
ultrafiltration membrane aided by flocculation and activated carbon treatments.
Desalination. 169, 257-267.
Huybrechts, D., De Baere, P., Van Espen, L., Wellens, B. & Dijkmans, R. (2002). Best
available techniques for carwash and truckwash, BBT study VITO:
http://www.emis.vito.be.
Lahoussine-Turcaud, V., Wiesner M.R. & Bottero, J.Y. (1990). Fouling in tangential-
flow ultrafiltration: the effect of colloid size and coaguration pretreatment. J.
Mem. Sci. 52, 173-190.
103
Metcalf & Eddy. (2003). In: Wastewater engineering treatment and reuse. pp. 1196-1202.
McGraw-Hill.
Nakajima, T., Kurosaki B. & Udagawa, H. (1986). Carwash wastewater treatment. Patent
No. 61020324, JP.
Okumura, M. & Onoue, K. (1978). In: Proc. 53rd Annual Meeting of Sen-i Gakkai,
Tokyo, 171.
Suzuki, M., Umehara, T., Tsukamoto, K. & Tsukahara, H. (2000). Recycle device of car
washing machine waste water and recycle method of car washing machine
guttation, Patent No. 2000000585, JP.
Toyozo, H. & Miyazaki, Y. (2004). Reuse of carwash water with a cellulose acetate
ultrafiltration membrane added by flocculation and activated carbon treatments.
Desalination. 169, 257-267.
Winfield, B. (1976). Waste treatment with reverse osmosis membranes. Mem. Sep.
Biotechnol. 1. 355-373.
104
6 Chapter 6:
Municipal Wastewater Treatment by Physico-Chemical
Processes
105
Abstract
Dilemmas like water shortage, rapid industrialization, growing human population and
related issues have seriously affected human health and environmental sustainability. For
conservation and sustainable use of our water resources, innovative methods for
wastewater treatment are continuously being explored. AOPs show a promising approach
to meet specific objectives of MWW treatment. The MWW samples were pretreated with
Al2(SO4)3•8H2O (Alum) at different doses 4, 8, 12 to 50 mg L-1 to enhance the
sedimentation. The maximum COD removal was observed at alum treatments in range of
28 to 32 mg L-1 without increasing TDS. TDS were found to increase when the alum dose
was increased from 32–40 mg L-1. In the present study, the optimum alum dose of 30
mg L-1 for 3 hours of sedimentation and subsequent integrated H2O2/UV treatment was
applied (using 2.5 ml L-1 of 40% waste H2O2 and 35% fresh H2O2 separately). Organic
and inorganic pollutants, contributing towards COD, BOD, turbidity and TDS were
degraded by H2O2/UV. About 93% COD, 90% BOD and 83% turbidity reduction
occurred when 40% waste H2O2 was used. After using fresh H2O2, COD, BOD and
turbidity reduction was 63%, 68% and 86% respectively. Complete disinfection of
coliform bacteria occurred by using 40% H2O2/UV. The most interesting part of this
research was to compare the effectiveness of waste H2O2 with fresh H2O2. Waste H2O2
generated from an industrial process of disinfection was found more effective in the
treatment of MWW than fresh 35% H2O2.
106
6.1 Introduction
Chemically enhanced methods, in conjunction with AOP provides an efficient and
promising alternative to conventional methods for the treatment of MWW. These
techniques can be used in combination with the conventional methods to increase the
overall performance of the wastewater treatment plant (WWTP). Various studies have
shown that AOPs can be utilized to decompose substances such as insecticides, dyes,
surfactants and organochlorides into relatively harmless substances such as carbon
dioxide and water (Fox, 1993; Yonar, 2006). Treatment with alum beforehand may
further enhance the wastewater treatment using AOPs. Velasco et al., (2007), studied the
effect of aluminum sulphate and Poly Aluminium Chloride (PAC1) as a coagulant for the
removal of dissolved organic carbon of surface waters. It was found that the efficiency of
alum was highly dependant on operational conditions such as pH and dose. The pH tends
to affect the solubility of aluminum in coagulation, which is favored under more acidic
conditions since acceptable residual aluminum concentration is achieved, whereas
aluminum solubility increases and therefore pH effect must be balanced (Sarkar, 2005).
ln another study, alum and aluminum hydroxide was used for the removal of phosphates
from wastewater, which are the major contributors of the eutrophication of water bodies
(Georgantas and Grigoropoulou, 2007). Alum was found to be a better chemical for
phosphate removal even though the active coagulant formed was Al(OH)3. Temperature
did not affect alum action but aluminum hydroxide showed variations with the change of
temperature.
In Tunisia, the DWW was proposed to be treated using H2O2 so as to meet the
problem of water shortage and recycle the wastewater for further reuse. According to the
research, 30% H2O2 increase the biodegradability of some water pollutants and an
optimum dose of 2.5 ml L-1 was sufficient to destroy majority of the risks even though it
may vary according to the amount of organic matter present in water. COD reduction
achieved was about 85%. Significant decrease in BOD5 was also observed as well as
exponential inactivation of fecal coliform was achieved (Verstaete, 1998; Ksibi, 2006;
Rosal, 2008). In another research, DWW was treated in batch and continuous mode using
H2O2/UV/O3. Beforehand, the water was pretreated using three different methods for
107
turbidity removal, which might hinder the effect of the latter treatment, namely; plain
sedimentation. The results showed that neither plain sedimentation nor filtration showed
substantial results, but aluminum sulfate at an optimum pH of 7 and optimum dose of 60
mg L-1 showed appreciable reduction in COD (39%) and turbidity (84%). This resulted
in better effluent COD as opposed to raw wastewater. No doubt, H2O2 concentration was
an important parameter, and the greatest decrease in COD was found to be at 100 mg L-1.
The process greatly reduced the reaction time due to UV lamps and enormous decrease in
the amount of residual COD. In addition, the water microbial count was also significantly
reduced (Yonar et al., 2006; Teresa et al., 2006). In another study, use of ozone increased
the level of hydroxyl radicals and increased the rate of degradation of organic pollutant in
DWW (Legrini et al., 1993).
However, the use of fresh H2O2 may be costly. Moreover, the H2O2 alone or in
combination with alum coagulation can not effectively remove microbial loads from
treated MWW which would be reused. The specific objectives of this study were to
compare the effectiveness of used and fresh H2O2 to treat the MWW and to reduce the
alum dose for chemical sedimentation. The combination of H2O2 with UV light was
investigated to observe the effectiveness of integrated treatment of organic matter.
108
specification of 240 – 280 nanometers, 16000 – 32000 microwatt-second per square with
water depth range 2 to 3 inches, brand light source USA.
109
6.2.4 Microbial count
The membrane filter technique was used for microbial analysis (Verstrate, 1998).
For this purpose, various dilutions (10-3 to 10-6) were made of the wastewater sample.
Nutrient agar (2%) was used as solidifying medium in sterilized petri dishes. 100 mL
diluted MWW sample was filtered through filter paper (0.45μm porosity) and incubated
at 35oC for 24 h. The colonies were counted under the compound microscope at
magnification power of 10-15 X (Results are not shown).
110
1) Domestic Wastewater collection (Sample)
Waste H2O2 40% (collected from Food Industry) and 35% fresh H2O2
111
(pH≈8). It seemed that pH values of MWW did not fluctuate significantly (p < 0.05) after
dosing with alum and subsequent treatment with H2O2 and thus should not be considered
in the process design.
Figure 6.2 Effect of fresh H2O2 treatment on pH with the passage of time
112
Figure 6.3 Decrease in turbidity after treating with alum and H2O2/UV, (Raw WW represents raw
wastewater, NS = Natural Sedimentation)
6.3.3 Effect on COD and BOD after treating with 35% fresh H2O2/UV and
40% waste H2O2/UV
Noteworthy reduction in the COD and BOD of the MWW was seen more
effective reduction by 40% waste peroxide treatment. Figure 6.4 shows that both BOD
and COD reductions were different when treating the wastewater samples with two
different concentration of peroxide separately. Natural sedimentation and alum treatment
had similar effects as shown in the Figure 6.4. Reduction in COD and BOD observed was
upto 87% and 89% after the 30 minutes mixing of 40% waste H2O2 and both parameters
reduced further to 96 and 90% after 60 minutes of mixing. After 120 minutes no further
decrease in COD and BOD was observed. COD reduction was very sharp with in 30
minutes mixing of 40% waste peroxide. Effective reduction in COD and BOD occurred
by treating same sample with 35% fresh H2O2 after 120 minutes of mixing. In this
treatment, the use of fresh H2O2/UV caused continuous decrease of COD and BOD
after120 minutes of mixing. While using waste H2O2/UV treatment, there was continuous
decrease in COD and BOD values till 60 minutes as 20 and 19 mg L-1, after 60 minutes
no further decrease was observed. It indicated that using waste H2O2 was effective for 60
minutes than fresh H2O2. Where as the obtained results of COD and BOD were 98 mg L-1
and 58 mg L-1 with fresh H2O2 showing effective results after 120 minutes. H2O2 is one
113
of the most powerful known oxidizer and results in the formation of hydroxyl radicals
(ºOH), which reacts with the pollutants such as iron, sulfide, solvents and gasoline as well
as pesticides present in MWW, thus, reducing the contamination level in water. UV
radiation provides the necessary energy for carrying the various chemical, physical and
biological processes for the oxidizing the pollutants. These oxidations entail an array of
direct and indirect photoreactions which are initiated by the absorbed UV radiation.
Moreover, UV light can also disinfect the water samples.
Figure 6.4 Reduction of COD and BOD after treating with 35% fresh and 40% waste H2O2 along
with UV light (Raw WW represents raw wastewater, NS = Natural Sedimentation)
Table 6-1 shows the characteristics of MWW prior to and after integrated
chemical treatment. A comparison of degradability of fresh and waste H2O2 has been
given in Figure 6.4. It is clear that when using 40% waste H2O2 with UV light, 30
minutes of mixing can be sufficient for the reduction of COD and BOD while fresh
peroxide with UV needs more than 2.5 ml of peroxide and a longer time to reach the 90%
removal efficiency. In another study (Kisibi, 2006) more than 90% COD removal
efficiency was achieved by 3 ml of fresh peroxide without using UV light. In previous
studies (Bhatti et al., 2009), alum alone was not sufficient to decrease COD and BOD.
114
6.3.4 Microbial activity
UV treatment with peroxide can easily inactivate, even with low H2O2 doses,
chlorine resistant species such as Giardia and Cryptosporidium which a dangerous human
pathogens. UV is a green technology as it is chemical free and produces no disinfection
byproducts. Hence, the most significant effect was observed during the inactivation of
fecal coliform, which decreased to 0 CFU/10ml after 60 minutes of peroxide/UV
treatment (Results are not indicated). Even after 30 minutes the microbial count had
fallen to 4 CFU/10ml of wastewater. Using primary and secondary wastewater treatment
processes alone for the reduction of enteric organism my results in 90-99.9% elimination,
and tertiary treatment may further decimate these pathogens, the treated wastewater could
still be contaminated by high microbial numbers. Henceforth, further disinfection of this
treated wastewater may be necessary. For this purpose, integrated H2O2/UV treatment
can be used.
The present investigation showed that CEPS may not be sufficient alone to treat
complex wastewaters especially industrial effluents. Some additional treatment
technologies especially anaerobic/aerobic treatments may be employed for the effective
treatment. Further research work is required to investigate the unit cost of operations.
6.4 Conclusions
The present study compared the effectiveness of used and fresh H2O2 to treat the
MWW and to reduce the alum dose for chemical treatment. The combination of H2O2
with UV light was found very effective to decrease BOD, COD, turbidity and coliform
bacteria in MWW. Waste H2O2 generated from an industrial process of disinfection was
found more effective in the treatment of MWW than fresh 35% H2O2. The waste H2O2
can be applied in combinations with UV light to treat MWW effectively.
115
References
APHA, American Public Health Association, Inc. (2005). Standard methods for the
examination of water and wastewater (21st Ed.), New York, USA.
Bhatti, Z. A., Mahmood, Q. & Raja, I. A. (2009). Sewage water pollutants removal
efficiency correlates to the concentration gradient of amendaments. J. Chem. Soc.
Pakistan. 31(4), 665-673.
George, T. (2004). In: Wastewater engineering treatment and reuse. pp. 1196-1200. 4th
edition.
Kisibi. M. (2006). Chemical oxidation with hydrogen peroxide for domestic wastewater
treatment. Chem. Eng. J. 119, 161-165.
Legrini, O., Oliveros, E. & Braun, A. M. (1993). Photochemical processes for water
treatmet. Chem. Rev. 93, 671-698.
Rosal, R., Rodriguez, A., Perdigon-Melon, J., Peter, A. & Garcia-Calvo, E. (2008).
Oxidation of dissolved organic matter in the effluent of a sewage treatment plant
using ozone combined with hydrogen peroxide (O3/H2O2). Chem. Eng. J. 149,
311-318.
Teresa, Z., Gunther, G. & Fernando, H. (2006). Chemical oxygen demand reduction in
coffee wastewater through chemical flocculation and advanced oxidation
processes. J. Env. Sci. 19(3), 300-305.
Velasco, U. & Juan, R. (2007). Enhanced coagulation under changing alkalinity- hardness
conditions and its implications on trihalomethane precursor’s removal and
relationship with UV absorbance. Sep. Purif. Technol. 55, 368 - 380.
Verstraete, W. (1998). In: Microbial ecology, practical course notes. pp. 20-30. Ghent
University Belgium.
116
Yonar, T., Kadir, K. and Nuri, A. (2006). Treatability studies on domestic wastewater
using H2O2/UV process, Applied Catalysis. Environmental. 67, 223-228.
117
7 Chapter 7:
Municipal Wastewater Treatment by Integrated System
118
Abstract
The UASB reactor was used to treat mixed MWW at hydraulic retention time 24-
48 hrs and at an average temperature 25-34ºC. The aim was to test two stage treatment
concept for low cost MWW treatment as UASB in first stage and waste H2O2 40% 2
ml L-1 of UASB effluent at second stage. Moreover, the effect of micronutrients on the
treatability of UASB was also investigated. After start up with glucose for first 15days
(first stage), the reactor was fed with macro and micronutrients as SNI for 45 days
(second stage). The maximum substrate removal rate was same 0.07 d-1 for both glucose
and SNI. Removal efficiency of TSS, COD, TN, ortho-P and turbidity as 73%, 99%,
84%, 19% and 67%. Waste H2O2 was found successful in NH4+ removal during post
treatment where 80% nitrogen was removed. Low cost integrated treatment using UASB
and H2O2 was found an excellent novel treatment choice for mixed MWW in developing
countries.
Key words: Anaerobic treatment, COD removal, MWW, post treatment, waste H2O2
119
7.1 Introduction
Up-flow anaerobic bioreactor (UAB) reactor has been used since last decade to
treat sewage water due to its easy and low operating cost. However to shorten its start up
period reactor is often inoculated with active microorganisms/ granules otherwise it takes
more than three months or longer to achieve full efficiency (Lettinga, 1993). Its
application can be more with renewable energy production when treating rich organic
wastewater such as food industry wastewater (Boe et. al., 2008; La Motta et al., 2008).
At present, The UAB system is facing challenges in shortens the start up period
and guarantee high purification efficiency. Some reasons for this can be ascribed to a lack
of information on selection of sludge, kinetics involved during start up of low and high
strength wastewater treatment. Environmental factors can also effect on process kinetics
and substrate removal (Singh, 1999).
The rate at which the organic matter converts or removes in any bioreactor is
governed by two main interconnected factors: the performance of the microbiological
processes and the hydrodynamics of the reactor. Biological wastewater treatment always
involves more than one phase working at the same time. In the normal operation of both
aerobic and anaerobic bioreactors, the liquid, solid and gaseous phases interact with each
other. Due to this, different factors such as mixing intensity, temporal and spatial
variations of mixing, degree of material segregation, gas bubbling pattern and intensity
all influence the hydrodynamic behavior of three phase reactors (Ottino and Khakhar,
2000; Bailey and Ollis, 1986). The hydrodynamic behavior of UASBs is also related to
the type of influent –feeding device, up flow velocity, sludge bed depth and sludge
120
blanket height. Van der Meer and Heertjes, 1983, assumed that the fluid which flow in
the settling compartments of an UASB followed a laminar regime and the sludge bed and
sludge blanket were completely mixed, although the sludge bed volume could also have
dead spaces, bypassing and returning flows (Pena, 2006). UASB reactor was found poor
removal of total ammonium nitrogen and total kjeldahl nitrogen 1 mg L-1 each in UASB
effluent (Aiyuk, 2004).
7.2 Objectives
The objectives of the study were to evaluate some kinetics parameters of UASB,
effect of glucose, effect of micro and macro-nutrients for reactor start up. To study the
treatment effect on total nitrogen and orthophosphate removal during post treatment of
AOP using 40% waste H2O2. The overall treatment concept proposed as Low Cost
Municipal Wastewater Treatment.
121
7.3 Materials and Methods
7.3.1 Start up of UASB reactor
The whole treatment process was performed in a room where maximum and
minimum temperature was observed 35ºC and 15ºC during May to June. Both reactor and
mixing tank were connected with tubing to transfer the liquid. Reactor and mixing tank
was constructed with 5 mm thick transparent acrylic material. Inner diameter 11.7 cm and
total height 43.5 cm and recycling effluent was collected from 36.5 cm height and total
volume 4.6 liters with working volume 4.4 liters. The reactor had total five ports, three at
upper most part on right and left side of the reactor which was used for effluent collection
and recycling of the effluent. Upper most right side port was used to collect UASB
treated effluent for chemical oxidation process and center top over port was left for gas
collection.
Furthermore clogging of recycle pipe may cause bursting of the pipe which can
spill the reactor effluent. Failure of main recycle pipe leads to direct the fluid through
overflow standpipe. Recycling increases the liquid up-flow velocity in the reactor and
dilutes the influent moving inside the reactor. Therefore re-adjusting the HRT may
require. Two liters capacity jar, made with acrylic material, received UASB effluent for
oxidation to polish the effluent by H2O2 in batch system. H2O2 was added at the rate of 2
ml L-1. Optimization of H2O2 was reported in chapter third and fourth.
The reactor started up with single nutrient glucose for fourteen days (stage I) at
HRT of 48 hrs. Reactor parameters are summarized in Table 7-3. Sludge was collected
from a domestic septic tank located near COMSATS University Abbottabad. It was
opened after 10 years of its working condition. Synthetic nutrient influent composition
has been shown in Tables 7-1 & 7-2. The pH was adjusted with 1N NaOH and HCl
solutions for synthetic glucose and macro and micro-nutrients solution. For the initial two
weeks, it was not fed with any nutrients and only glucose was fed as carbon source. After
15 days, it was fed with micro and macronutrients (Stage II). Reactor was kept in a
separate room with day and night temperature fluctuations of 10C (20-30C) and it was
operated in a continuous mode. After 39 days HRT was reduced to 24 hrs from 48 hrs
with same loading rate to see the effect of glucose, macro and micro-nutrients. After
122
achieving stable COD removal of 99.90%, it was shifted to MWW and later on food
industry wastewater, which was being discharged directly into sewage system.
S S e
U
.X
(1)
Fb
BODe
0.65 CODe
(2)
S Se
E o 100
So
(3)
BOD5 bCOD
Fb
0.65 COD COD
(4)
Where, U= specific substrate utilization rate (d-1); = HRT (h); So= influent COD (mg
L-1); Se= effluent COD (mg L-1); X =average VSS (mg L-1) concentration in reactor;
Fb = biodegradable fractions; BODe= Five day biochemical oxygen demand of effluent
(mg L-1), CODe = Chemical oxygen demand of effluent (mg L-1), E = removal efficiency
in (%) Fb = biodegradable fraction, bCOD= biodegradable chemical oxygen demand
(Mathiewu, 2000; Verstraete, 2005).
123
fed to the UASB reactor. The glucose solution was prepared as 0.5 g L-1 in distilled water
with average obtained COD 250–300 mg L-1.
Table 7-1 Composition of synthetic influent (SNI)
Parameter Value
Temperature (ºC) 20-30
Volume of reactor (L) 4.6
Volume of influent (L d-1 ) 2.16
Concentration of influent (mg COD L-1 ) 300-350
Mass loading rate (g COD L-1 hr-1 ) 0.144
Hydraulic loading rate (L L-1 day-1) 0.48
Hydraulic retention time (hrs) 48
Upflow velocity (cm h-1) 0.05
These nutrients (MgCl2, KH2PO4, (NH4)2SO4 and trace elements) were compared with
glucose fed as influent nutrients in reactor.
124
7.3.3 Analytical procedures
All the analytical procedures used were the standard methods for water and
wastewater analysis (APHA, 2005). Wastewater samples were analyzed prior to and after
the treatment with UASB and 40% H2O2. COD was determined by closed reflux
colorimetric method using digester (HACH - LTG 082.99.40001), (APHA, 2005), the
wastewater sample, digestion solution and sulphuric acid were digested in vials for two
hours at 150oC. After digestion, absorbance was measured at wavelength 605 nm in a
spectrophotometer (LOVIBOND tintometer GMBH, 44287 DORTMUND). The pH was
measured immediately after collection without stirring to prevent loss of CO2 from the
sample; such losses may cause changes in pH. The pH meter (HANNA, HI – 991003)
was used for determination. H2O2 was measured according to Tetra Pak Technical data
manual by using hydrometer and temperature. H2O2 value was obtained after connecting
temperature and hydrometer reading on third scale of H2O2 W/W (Tetra Pak, 2008).
Figure 7.1 UASB followed by chemical oxidation with 40% hydrogen peroxide. P1= peristaltic feed
pump, P2 = peristaltic recycle pump
Kjeldahl nitrogen is the sum of organic nitrogen and ammonia nitrogen. Semi-
micro-Kjeldahl method (4500-Norg) digestion was performed for one hour and two at 200
and 300ºC followed by distillation was used where sum of organic and ammonia nitrogen
was measured. For NO3 and NO2 WAGSTECH KIT was used for determination.
Ammonia was measured by titrimetric method (4500-NH3 C).
125
7.4 Results and Discussions
7.4.1 Effect of glucose during UASB start up period
Concentration of glucose was added at rate of 0.5 g L-1 in tap water which was
equivalent to COD value of 250-350 mg L-1. Reactor efficiency was monitored to check
the effect of glucose on its reduction of startup period. Reactor sludge was allowed to
grow on glucose as substrate for first 15 days.
Figure 7.2 pHi (influent), pHe (effluent) comparison during start-up of UASB, using glucose as a sole
nutrient
Figure 7.3pHi and pHe comparison for synthetic influent used for startup after addition of
micronutrients
126
It was observed that reactor pH remain between 7 and 7.5 till day 6 and decreased to
below 6.7 during days 7th–14th, which was a clear indication of acid formation. No
acidification was observed during first 5 day and later immediate decline in pH was
observed due to acid formation (Vadlani, 2008). The pH was monitored regularly for
influent and effluent from day 1 to 15 when only glucose was added as nutrient. The
changes in pH were observed after two days when influent pH was 7.3 and same day
effluent pH was observed 7.4. The effluent pH remained higher than the influent pH till
day 5 and after 7th day it dropped very sharply and remains below than influent value till
day 14 (Figure 7.2).
The maximum COD removal was observed around pH 7 even during start up of
reactor (first fourteen days with glucose as nutrient) where COD removal efficiency was
less than 70%. It was observed COD removal efficiency improves with pH above 6.8
feeding SNI. Same trend of pH was observed during first week of start up with glucose
influent and SNI.
127
In Figure 7.5 where comparison of COD removal efficiency has been indicated of
glucose influent which shows acceptable removal of COD after six days and it remained
below 100 mg L-1 but removal efficiency did not exceed 80%. In study by Subramanyam,
2007 using glucose as a primary nutrient for start up, 75% COD removal was observed
during start up.
In another study by Zhou, 2006 UASB reactor was fed by three kinds of different
substrates, glucose, skimmed milk and mixed volatile fatty acids (VFAs). In this study
extracellular polymer production was investigated with surface charge of different
substrate which effect on granulation. The pH was adjusted to 7.4 in mesophillic
conditions, big stout granules formed with glucose as substrate. The maximum COD
removal efficiency was achieved 90%. In another study where sucrose was fed with
diluted leachate to the laboratory scale UASB reactor, sucrose was also found to be
decreasing the pH of the reactor from 7.2-4.7 which inhibit the reactor efficiency (Eng,
1986). Sucrose as reducing sugar converts into glucose and fructose where glucose was
further used as carbon source. Glucose as carbon source was also studied by Majumder,
2007 to treat wastewater containing 2-chlorophenol and 2,4-dichlorophenol. Glucose was
observed good carbon source and removal efficiency of 2-chlorophenol was 93.7%. This
showed that glucose was much better carbon source to remove 2-chlorophenol and
highest gas production 76.1% as compared to other carbon source nutrient used. Sodium
128
formate, sodium propionate, glucose and methanol were used separately in the feed as co-
substrate.
Figure 7.6 COD influent and COD effluent form fifteenth day with SNI
The most interesting results of COD removal 80% in present study were achieved
after one week of reactor start up using only glucose as carbon source for the
microorganisms. Glucose served as better carbon source which was easily biodegradable
to form acetate and good carbon source for active biomass. As compared to other studies
where glucose was used as carbon source during start up of reactor for 1) granulation, 2)
removal effect of specific compounds and 3) removal of COD and other studies showed a
maximum COD removal rate of 75% where reactor was seeded from full scale UASB
reactor.
During second stage start up process where synthetic influent was used in same
reactor (Figure 7.6) it was clear that COD removal was more than 90% and after 30 day
of start with synthetic influent COD removal was 95% and it remained till 49 days.
Comparing glucose and SNI (Figure 7.9) during start up showed that using glucose as
influent (first stage) removed COD value of 70% while in SNI (Second stage) influent
COD removal was > 95% during first 30-45 days. After 19 days of feeding with SNI,
effluent COD was below 50 mg L-1 and after 31 day effluent COD was detected < 4 mg
L-1.
129
Figure 7.7 Percent COD removal using SNI in UASB
HRT was maintained 48 hr for both glucose and SNI. Glucose in synthetic wastewater
increased the specific methanogenic activity (Vadlani, 2008). COD removal efficiency
was found much greater with SNI than glucose only (Figure 7.5, 7.6). Percent COD
removal was indicated in Figure 7.7 from day 15 to 45 during second stage.
Study by Kalogo (2001); Kalogo and M’Bassiguie (2001) on self inoculated
reactor treating domestic wastewater, the reactor achieved a removal efficiency of up to
65% of COD and 73% suspended solids and indicated that removal of matter was mainly
due to interception in the reactor. Many studies have mentioned that UASB digesters
need to be inoculated with flocculent sludge whereas self-inoculation was another
alternative for start-up. Without using seed during start-up of reactor considered to be
feasible after 6 – 12 weeks at HRT about 6 h and temperature above 20ºC (Lettinga et al.,
1993). In another study by Alvarez, (2006) start-up without inoculum for 120 days, 58%
total COD removal at temperature 15ºC and HRT 11 hrs. It is concluded from present
research self inoculated UASB reactor can achieve the maximum COD removal
efficiency in 4 weeks if sludge was used from domestic septic tank. No granules were
observed in four weeks period and maximum removal efficiency was achieved.
7.4.3 Substrate uptake rate during start up with glucose and SNI
Yield coefficient was supposed to be constant due to same feeding rate of glucose
as COD 250-300 mg L-1 was added. In this experiment a slight drop in pH was observed
130
due to glucose conversion to acid as indicated in Figure 7.2. During first five days
substrate uptake rate was lower and COD was higher in effluent more than 100 mg L-1.
After five days substrate uptake rate increased and effluent COD started to decrease at
same rate. After six days there was maximum removal of substrate uptake was observed
and with a maximum COD removal. During first five days active biomass was not
present therefore substrate uptake rate was low. With continuous feed of substrate at
same flow rate and concentration non-active biomass was washed out from anaerobic
reactor. At the same time, active biomass increased which accumulated inside the reactor.
This substrate uptake rate helped in adaptation of specific activity like enzyme production
for degradation of volatile fatty acids (VFA) (Vadlani, 2008). Specific uptake rate was
calculated from VSS, HRT and reactor volume. Substrate uptake rate improved after 6th
day and remained same till 14 days (Figure 7.8). If mass loading rate, upflow velocity or
HRT increased, active biomass may wash or need to acclimatize with new load.
Typically bacteria with a high substrate affinity (low Ks) found to be less efficient than
those who have low substrate affinity but high Ks value (Verstrate, 2004). This was
proved from Figure 7.8 where substrate uptake rate increase after four days for glucose.
SNI uptake increased after 22 days and COD removal rate was observed 99% while 80 –
85% for glucose solution. Anaerobic species in reactor having high affinity with glucose
(stage I) as compare to SNI where anaerobic species showed less affinity with SNI but
removal rate of COD was higher than glucose. After 20 days, reactor reached to its full
efficiency but it was kept feeding with SNI till 35 days to make this reactor ready for
MWW. This MWW had very uncertain variation in COD values due to industrial
discharge in sewage system. It was observed that affinity with substrate was very
important for the maximum COD removal efficiency and to shorten start up period for
the maximum COD removal rate. Other researchers have not reported the effect of
substrate affinity on COD removal. Low substrate affinity may have positive effect on
COD removal than those with high substrate affinity. In present study it was observed
synthetic nutrients gave low substrate affinity than glucose. It may be possible that
glucose quickly assimilate in microbial cells and after 7 days uptake rate was slow while
SNI was very effective in assimilation of nutrients present in SNI. This experiment was
conducted to replace blend of different nutrients with single carbon source (glucose) and
131
it proved that single glucose may not be enough to reduce the reactor start-up time and
COD removal efficiency (Figure 7.9). Start up with SNI was found in 35 days with COD
removal efficiency 99.9%.
132
Figure 7.10 SNI effects on biodegradable fraction and substrate uptake rate.
133
Stage I, when only glucose feeding was studied for fourteen days biodegradeable
fractions and substrate uptake was compared in Figure 7.8 and Figure 7.11 during
glucose feeding for 14 days. In these figures it is clear substrate uptake rate increased
after 6 days but there was no clear decrease in biodegradeable fractions except day 10
where Fb 0.7 and other 13 days it remained in range of 0.8 and 0.9. In case of SNI, Fb
decreased after 19 days and remain below 0.5 in Figure 7.10. It is fraction which is as
readily accessible as molecules such as glucose and acetate (Verstraete, 2004). In
untrated MWW these fractions are normally found greater than 0.9 and it should be
below 0.4 after biological treatment. During first three days glucose uptake rate was less
and effluent may contained a Fb from influent and sludge washing. After five days
substrate uptake rate was same from 0.06 – 0.08 per day. On 10th day there was only one
value obtained with minimum biodegradable fraction found in effluent, which seems to
be not normal as compared with (Fb and U) other values obtained during 14 days.
VSS/TSS ratio decreased to 0.65 from 0.9 after 7 days and then remained below 0.4.
134
Table 7-5 Average characteristics of raw MWW and effluent of various treatment steps. BDL =
Below detection limit
Ammoinium nitrogen which is toxic to aquatic species was oxidized with H2O2.
Table 7-6 showed that there was decrease in ammonium nitrogen after 30 minutes of
mixing but later on it was found slight increase in its concentration and after 120 minutes
0.1 was observed. Nitrate nitrogen was only parameter which was found increasing as
reaction proceeded and nitrite and ammonium nitrogen were foud decreasing with
mixing time. It seemed that nitrification was more dominant than denitrification. It was
also reported that some chemical has been already used for nitrification and
denitrification process. Sabzalim, 2006 reported denitrification of nitrate using Zn and
sulfamic acid treating ground water.
135
with zeolite are two hours mixing and recharging of used zeolite. In this study NH4+ was
passed through a column charged with 1.2 kg of zeolite system attached after UASB
reactor proved to be efficient with 99% removal than the zeolite column installed before
UASB reactor, 47% efficiency (Aiyuk, 2004). In another study by El-Shafai (2007),
where duck weed ponds were used after UASB reactor to remove NH4+ with 98%
efficiency. The disadvantage of this system is only that it requires large area for
duckweed ponds where three ponds were used to achieve efficiency. In the present study
waste H2O2 was used after UASB reactor to meet discharging standards. Possible
reaction after addition of H2O2 as given below, ammonium was converted into nitrate
which was less toxic (Table 7-6, Figure 7.12).
Table 7-6 UASB effluent treatment with H2O2 at optimized dose 2.0 ml L-1
Over all total nitrogen removal was 84% with effluent concentration was 5 mg L-1 after
peroxide treatment which was value below the permissible limit of Pakistan
environmental protection Agency (PEPA) discharging standards. The maximum nitrogen
removal was observed after peroxide treatment which might be due to post treatment of
oxidation process.
136
and it was 74 mg L-1 at 24 hrs HRT with 99% removal efficiency. No change was
observed in turbidity, TDS, conductivity and pH. Other parameters were required to
study more to see the effect on total nitrogen after UASB. Many researchers have worked
to see the effect on treatment efficiency at lowest HRT. Mahmood (2007) observed 85%
nitrate removal efficiency with zero ammonia in effluent at 24hrs HRT and sulfide
removal 99% at 0.1day HRT. In this study sludge was collected from anaerobic
methanogenic reactor. In present research work 85% total nitrogen and 95% ammonia
removal was observed at HRT 1-2d where inoculum was collected from domestic septic
tank.
Figure 7.12 Effect on ammonium, nitrate and nitrite after treating UASB effluent with H2O2
Table 7-6 shows that UASB reactor achieved full efficiency in shorter time period
when granular sludge was selected during start up other wise it take three months to
achieve maximum efficiency (Yu, 2001; Zhou, 2006; Kalogo, 2001). It is clear from
Table 7-7 during start up of UASB reactor the maximum removal efficiency of 95% was
observed with cattle manure as inoculums. it is clear from present research that domestic
septic tank sludge achieved the maximum COD removal efficiency of 95-99% in only
eight weeks at HRT of 24-48 h. Granulation was not included in this part of the study due
to mixed MWW was used. Many researchers have indicated that maximum removal
137
efficiency relates with granulation formation which takes three months. It is clear
domestic septic tank sludge could be very effective in removal of COD form domestic
and MWW unless it was not mixed with other industrial toxic wastewater.
138
Table 7-8 The economic analysis of various treatment options for MWW
7.6 Conclusions
During start up of UASB, glucose and SNI were used to activate the acetogenic
and methanogenic microbial species. These species were found low affinity with SNI and
high affinity with glucose which resulted in treatment efficiency was higher in removing
COD from 95% and 85%. These influents, SNI and glucose solution was fed separately
to the reactor for 1–14 days (phase I) and 15–45 days (Phase II). This system was
139
designed to face broad variations in COD feed because MWW contained both industrial
and domestic wastewater.
In this study combination of UASB with AOP was tested to see the effect on
COD, TN and Ortho-P. This proposed system was found very successful in removal of
COD 99% and TN 84% at low investment cost. Orhto-P removal did not reach up-to
working goal. In this regard phosphorus and nitrogen both were not in ratio 15:1 for
eutrophication. As proposed treatment system was successful to reduce total nitrogen to
acceptable limits which could be effective to obstruct eutrophication. Excessive Ortho-
phosphorus alone has less consequence on eutrophication. In this regards combining
UASB with waste 40% H2O2 was to contrive successful combination with less treatment
cost. This combination was successfully used to treat MWW in the laboratory with of
67% turbidity removal, 95% ammonium, 85% VSS, 84% Total nitrogen and COD 99%
removal.
Addition of AOP after UASB was found very successful in order to reduce the
nitrogen species by oxidation process. Optimized dose of 2 ml L-1 of 40% H2O2 was used
to treat UASB effluent. There was poor ortho-phosphorus removal by UASB treatment.
Considerable work in this regard was to use waste H2O2 to polish the UASB effluent by
reducing TN, Turbidity and microbial load.
140
References
Aiyuk. S., Amoako. J., Raskin. L.,VanHaandel. A. & Verstraete. W. (2004). Removal of
carbon and nutrients form domestic wastewater using a low investment, integrated
treatment concept. Water Res. 38, 3031-3042.
Akila, G. & Chandra, T.S. (2007). Performance of an UASB reactor treating synthetic
wastewater at low temperature using cold adapted seed slurry. Process Biochem.
42, 466-471.
Alvarez, J. A., Ruiz, I., Gomez, M., Presas, J. & Soto, M. (2006). Start-up alternatives
and performance of an UASB pilot plant treating diluted municipal wastewater at
low temperature. Bioresource Technol. 97, 1640-1649.
APHA, American Public Health Association, Inc. (2005). Standard methods for the
examination of water and wastewater (21st Ed.), New York, USA.
Bailey, J. E. & Ollis, D. F. (1986). In: Biochemical engineering fundamentals. McGraw-
Hill int, Nw York.
Bodkhe, S.Y. (2009).A modified anaerobic baffled reactor for municipal wastewater
treatment. J. Env. Manage. 90, 2488-2493.
Boe, K., Steyer, J. P. & Angelidaki, L. (2008). Monitoring and control of the biogas
process based on propionate concentration using online VFA measurement, Water
Sci. Technol. 57(5), 661-666.
Cohen, A., Breure, A., Van Andel, J. G. & van Deursen, A. (1982). Influence of phase
separation on the anaerobic digestion of glucose-II: stability and kinetic reponse
to shock loadings. Water Sci. Technol. 57(5), 687-692.
Dold, P. L., Bagg, W. K. & Marais, GvR. (1986). Measurement of the readily
biodegradable COD fraction (Sbs) in municipal wastewater by ultrafiltration
UCT, Report No. W57., Department of civil engineering, university of Cape
Town, Rondebosh, 7700, South Africa.
El-Shafai, S. A., El-Gohary, F. A., Nasr, F. A., Van der Steen, N. P. & Gijzen, H. j.
(2007). Nutrient recovery from domestic wastewater using a UASB-duckweed
ponds system. Bioresource Technol.. 98, 798-807.
Eng, S. C., Fernandes, X. A. & Paskins, A. R. (1986). Biochemical effects of
administering shock loads of sucrose to a laboratory-scale anaerobic (UASB)
effluent treatment plant. Water Research. 20, 789-794.
Kalogo Y., MBouche, J. H. and Verstraete, W. (2001). Physical and biological
performance of self inoculated UASB reactor treating raw domestic sewage. J.
Environ. Eng. 127 (2), 179-183.
141
Kalogo, Y., M’Bassiguie, A. & Verstraete, W. (2001). Enhancing the start-up of a USB
reactor treating domestic wastewater by adding a water extract of Moringa oleifer
seeds. Appl. Microb. Biotechnology. 55, 644-651.
La Motta, E. J., Padron, H., silva, E., Luque, J., Bustillos, A. & Corzo, P. (2008). Pilot
plant comparison between the AFBR and the UASB reactor for municipal
wastewater pretreatment. J. Env. Eng. 134(4), 265-272.
Lettinga, G., de Man, A., van der Last, A. R. M., Wiegant, W., van Knippenberg, K.,
Fijns, J. & Van Buuren, J. C. L. (1993). Anaerobic treatment of domestic sewage
and wastewater. Water Sci. Technol. 27(9), 67-73.
Mahmood, Q., 2007, Process performance, optimization and microbiology of anoxic
sulfide biooxidation using nitrite as electron acceptor, PhD dissertation. pp. 44-69.
Majumder, P. S. & Gupta, S. K. (2007). Effect of carbon sources and shock loading on
the removal of chlorophenols in sequential anaerobic-aerobic reactors.
Bioresource Technol. 99, 2930-2937.
Mathiewu, S. & Etienne, P. (2000). Estimation of wastewater biodegradable COD
fractions by combining respirometric experiments in various So/XO ratios. Water
Res. 34 (4), 1233-1246.
Methanol, (2009), http://www.methanol.org/pdf/MethanolDenitrification.pdf
Nikolic, A. & Hultman, B. (2005). Chemical denitrification for nitrogen removal from
landfill leachate. Water Sci. Technol. 52(10-11), 509-516
Pena, M. R., Mara, D.D. & Avella, G. P. (2006). Dispersion and treatment performance
analysis of an UASB reactor under different hydraulic loading rates. Water Res.
40, 445-452.
Ramakrishnan, A. & Gupta, S.K. (2006). Anaerobic biogranulation in a hybrid treating
phenolic waste. J. Hazard. Mater. B137, 1488-1495.
Sabzalim, A., Gholami, M., Yazdanbakhsh, A., Musavi, B. & Mirzaee, R. (2006).
Chemical denitrification of nitrate from groundwater via sulfamic acid and zinc
metal. Iran. J. Env. Heal. Sci. Eng. 3(3), 141-146.
Singh, K.S., Harada, H. & Virarghavan, T. (1996). Low strength wastewater treatment by
a UASB reactor. Bioresource Technol. 55, 187-194.
Singh, R. P., Kumar, S. & Ojha, C. S. P. (1999). Nutrient requirement for UASB process:
a review. Biochem. Eng. J. 3, 35-54.
Speece, R. E. (1996). In: Anaerobic biotechnology for industrial wastewater. pp. 31-57.
Archae press, Nashville, Tenn.
142
Subramanyam, R. & Mishra, I. M. (2007). Biodegradation of catechol (2-hydroxy
phenol) bearing wastewater in an UASB reactor. Chemosphere. 69, 816-824.
Tetra Pak Technical data manual. (2008). Hydrogen peroxide, Doc. No.OM-2771726-
0101, 8-9.
Vadlani, P. V. & Ramachandran, K. B. (2008). Evaluation of UASB reactor performance
during start-up operation using synthetic mixed-acid waste. Bioresource Techno.
99, 8231-8236.
Van der Meer, R. R. & Heertjes, P. M. (1983). Mathematical description of anaerobic
treatment of wastewater in upflow reactors. Biotechnol. Bioeng. XXV, 2557-
2566.
Van Hulle, S. W. H. (2005). Modelling simulation and optimization of Autotrophic
nitrogen removal processes. PhD thesis. pp. 8-9.
Verstraete, W. (2005). In: Environ. Biotech. Proc. pp. 1-30. Ghent University, Belgium.
Yu, H. Q., Fang, H. H. P. & Tay, J. H. (2001). Enhanced sludge granulation in upflow
anaerobic sludge blanket (UASB) reactors by aluminum chloride. Chemosphere.
44, 31-36.
Zhou W., Imai, T. Ukita, M., Sekine, M. & Higuchi, T. (2006). Triggering forces for
anaerobic granulation in UASB reactors. P. Biochem. 41, 36-43.
143
8 Chapter 8:
Sequential Two Stages Anaerobic and H2O2 Treatment of
Confectionary Wastewater
144
Abstract
Anaerobic treatment in combination with post treatment of advanced oxidation
process was employed to test the treatability of integrated process for confectionary
wastewater mixed with MWW. Reactor was inoculated with 10 year old septic tank
sludge and started up with glucose, macro and micro nutrients. The system was operated
at 25-30ºC, HRT 48 hrs for 25 days with post treatment with 40% waste H2O2. This
waste H2O2 was collected from industrial process after disinfection of packaging
material. Reactor performance was evaluated by pre and post treatment analysis of COD,
TSS, TDS, and turbidity. Their removal efficiencies were up to 98.6%, 91%, 50% and
81%, respectively. Reactor achieved its full efficiency after feeding diluted wastewater as
1/5, 1/3, 1/2 and 1/0 for 5 – 7 days each. Reactor achieved full efficiency in 25 days
removing 98% COD from mixed wastewater. A batch peroxide treatment process was
also added to reduce the turbidity and to increase the DO of treated effluent. The strategy
was found quite applicable for the treatment of combined industrial and municipal
effluents.
Keywords: Anaerobic reactor, advanced oxidation process, macro and micro nutrients,
dissolved oxygen, hydraulic retention time.
145
8.1 Introduction
Confectionary industries are growing very fast in Pakistan for their acceptable
products both for children and elder of all ages. Quantity of wastewater produced by
these industries is not as high as produced by other food industries but organic pollutant
load is very high, which is a major problem of this wastewater. Such wastewater if
discharged into normal sewage system or surface water then it rapidly increases the COD
and decrease the DO of water bodies. This high load of COD reduces the aesthetic values
of freshwater system (Spellman, 2003).
Effluent from UASB can be further treated to remove turbidity, COD, microbial
load and increase DO. In this study 40% waste hydrogen was used, which was collected
from nearby industry where it was used to disinfect the juice packaging material and then
after use it was discharged into sewage drains. This discarded 40% waste H2O2 was
tested on UASB effluent to polish it. Addition of neutralizing agents is needed for
146
confectionary wastewater, caustic normally used to adjust the pH close to neutral. It can
be an extra operational cost in this system (Romli et al., 1994).
2) To study the feeding effect of diluted wastewater, 1/5 dilution, 1/3 dilution, ½
dilution and undiluted, to achieve treatment efficiency in short time,
147
Table 8-1 Parameters used to treat industrial wastewater
Parameter Value
Temperature (ºC) 20-30
Volume of reactor (L) 4.6
-1
Volume of influent (L·d ) 2.16
Concentration of influent (mg COD· L-1 ) 300-2500
-1
Mass loading rate (g COD L . hr) 0.144
-1
Hydraulic loading rate (L·L .day) 0.48
Hydraulic retention time (hrs) 48
-1
Upflow velocity (cm·h ) 0.05
Figure 8.1 UASB followed by chemical oxidation with 40% hydrogen peroxide. P1= peristaltic feed
pump, P2 = peristaltic recycle pump
148
After digestion, absorbance was measured at wavelength 605 nm in a
spectrophotometer (LOVIBOND tintometer GMBH, 44287 DORTMUND). The pH was
measured immediately after collection without stirring to prevent loss of CO2 from the
sample, such losses may cause increase in pH. The pH meter (HANNA, HI – 991003)
was used for determination. H2O2 was measured according to Tetra Pak Technical data
manual by using hydrometer and temperature. H2O2 value was obtained after connecting
temperature and hydrometer reading on third scale of H2Os W/W (Tetra Pak, 2008).
Direct feeding of high organic load may be risky to wash out sludge from the
reactor. The maximum removal efficiency was observed after seven days but after 5 days
removal efficiency decreased again. The effluent from UASB was further treated with
waste 40% H2O2 to further improve the effluent quality. During first five day of
149
secondary treatment with peroxide was found very effective and maximal 22% removal
was observed. Later on till day 25 continuous decrease was observed in removal
efficiency with H2O2. Peroxide treatment was performed at the rate of 2 ml L-1 of UASB
effluent for sixty minutes of mixing. There was interesting removal rate shown in the
Figure 8.2, 8.3 where COD removal by peroxide and UASB reactors were similar.
Improving removal efficiency was observed in second week. From day 8 to 12 influent
was diluted with 70% distilled water and 30% sample. The maximum removal of 92%
was observed by anaerobic reactor during second week and only 1 to 5% was observed
for H2O2 treatment. During week 3rd anaerobic COD removal efficiency was increased
upto 94 to 96% and total COD removal after treating with H2O2 was 98%. This increase
in COD removal during 4th week achieved was considerable as the organic load increased
after conditioning of the reactor sludge with passage of time. HRT was kept 24 hr
throughout to see the effect of dilution effect on biomass to acclimatize the specific
carbohydrates rich wastewater. After three weeks it was observed that reactor was ready
to be fed with high strength wastewater. The only disadvantage seen through these
experiments was to increase in 10% sludge volume after four weeks. The COD removal
efficiency was also investigated by Beal (2000) where two anaerobic reactor UASB and
down flow anaerobic filter was used. In present study we used waste 40% H2O2 which
was found more effective than fresh available one. Using waste H2O2 was found more
effective to inactivate the microbes and increase in DO. UASB effluent has almost no DO
with high microbial load (results not shown). There was another advantage to use waste
H2O2 was 80% reduction in turbidity while only 28% turbidity removal efficiency was
found for UASB (Table 8-3).
150
Table 8-2COD removal comparison, in COD mg L-1
151
Table 8-3 Treatment efficiency
UASB %
Raw UASB H2O2 treatment Treatment
Parameters treatment
ww effluent 2 ml L-1 efficiency
efficiency
Figure 8.2 COD influent, UASB effluent and H2O2 treated effluent with COD removal mg L-1. PI
=Phase one, PII= Phase two, PIII= Phase three, PIV= Phase four, PV= Phase five.
152
Figure 8.3 COD removal efficiency, peroxide COD removal can be considered as total COD percent
removal
The pH adjustment was done with 1N NaOH before feeding to the anaerobic reactor.
Due to recycling, rapid biomass accumulation was observed where volume of the sludge
was increased 10% after 20 days when influent fed to reactor without dilution. Biomass
measurement was made during the last days of sample
treatment.
153
Organic loading rate (OLR) was increased gradually from diluted sample to
undiluted, during first week OLR was 0.144 g L-1 d-1, second week 0.288 g l-1, second
last week 0.518 g l-1 d-1 and last week 1.2 g l-1 d-1. Increase of VSS/TSS ratio of the
UASB reactor from 0.38 to 0.53 was observed in the last week of reactor operation which
was actually an increase in of active biomass. VSS are useful in control of wastewater
treatment operation because it offers a rough approximation of the amount f organic
matter found in solid fraction of wastewater, sludge and industrial waste.
2 H2O2 2H2O + O2
H2O2 is unstable and breaks down into single oxygen atom and a water molecule.
Atomic oxygen is very reactive that forming stable oxygen molecule increase the level of
dissolved oxygen (Hinchee, 1991). This atomic oxygen also degrades the remaining
organic matter left after UASB treatment. Due to its bleaching effect turbidity was
reduced to acceptable limits. UASB effluents do not contain dissolved oxygen. Post
treatment with H2O2 can regain the dissolved oxygen upto 6 ppm (Bhatti, 2009). Peroxide
converted the ammonium nitrogen to nitrate nitrogen. In water ammonia is present in un-
ionized and ionized form depending on pH and temperature. It is toxic for the more
sensitive salmon fish (see Table 8-4). H2O2 had been used in many studies to treat dyes in
textile industrial wastewater. Where it was reported to decolorize upto 90% of dyes using
large quantity (20 dm3) wastewater (Perkowski, 2003; Lettinga, 1978). Due to
154
effectiveness of oxidative reactions of H2O2, it proved to be effective in reduction of
turbidity, deodorization and disinfection of domestic and industrial wastewater treatment
(Yonar, 2006). H2O2 converts the ammonium nitrogen to nitrate which is less toxic to
aquatic species. Another economical approach studied by (Aiyuk, 2004; Kalogo, 2001)
was using zeolite to remove ammonium nitrogen.
Table 8-4 Lethal ammonia concentrations at different pH, and its exposure
This option had a disadvantage that zeolite needed recharging. In present study H2O2 was
used that just required single dose of 2 ml L-1of application and complete mixing.
155
Table 8-5 Treatment efficiency comparison of different investigators treating carbohydrate type
wastewater on the basis of COD percent removal
COD Treatment
Reactor
Author Year -1 efficiency, Wastewater type
type mg L percentage
UASB Cail and Barford 1985 27000 > 70 cane juice
UASB Driessen et al., 1995 22000 88 sugar cane juice
UASB Hawkes et al., 1995 50000 70 sugar cane molasses
UASB Beal et al., 2000 30000 98 confectioanry plant
UASB Gohil et al., 2005 15000 95 tomato processing
biscuits and
UASB Present study 2009 25000-30000 98.6
confectionary
UASB Lapisto et al., 1997 9000-27600 90 carrot blanching
8.4 Conclusions
Confectionary wastewater contains high load of organic mostly starch which is
used as major ingredient in candy production. UASB treatment was found to achieve
98% COD removal after 25 days. During 25 days wastewater dilution was fed to
gradaully acclimatize the anaerobic species to high loading of organic industrial waste.
The system was fed as 0.00144 kg COD·L-1.d-1S. hr at hydraulic retention time of 24 hrs.
the reduced COD was 48 mg L-1 which met discharging standards of NEQs.
156
References
Aiyuk, S., Amoako. J., Raskin. L., VanHaandel. A. & Verstraete. W. (2004). Removal of
carbon and nutrients form domestic wastewater using a low investment, integrated
treatment concept. Water. Res. 38, 3031-3042.
APHA, American Public Health Association, Inc., Standard methods for the examination
of water and wastewater (21st Ed.), New York, USA.
Bhatti, Z. A., Mahmood, Q. & Raja, I. A. (2009). Sewage water pollutants removal
efficiency correlates to the concentration gradient of amendaments. J. Chem. Soc.
Pakistan. 31(4), 665-673.
Cail, R. G. & Barford, J. P. (1985). A comparison of an upflow floc (tower) digester and
UASB system treating cane juice stillage. Agri. Wastes. 15, 291-299.
157
Kalogo, Y., MBouche, H. J. & Verstraete, W. (2001). Physical and biological
performance of self-inoculated UASB reactor treating raw domestic sewage. J.
Env. Eng. 127, 179-183.
Ksibi, M. (2006). Chemical oxidation with hydrogen peroxide for domestic wastewater
treatment. Chem. Eng. J. 119, 161-165.
Lapisto , S.S. & Rintala, J. A. (1997). Start-up and operation of laboratory scale
thermophilic anaerobic sludge blanket reactors treating vegetable processing
wastewater. J. Chem. Techno. Biot. 68, 331-339.
Romli, M., Greenfield, P.F. & Lee, P.L. (1994). Effect of recycle on a two-phase high-
rate anaerobic wastewater treatment system. Water Res. 28(2), 475-482.
Seghezzo, L., Zeeman, G., VanLier, J. B., Hamelers, H. V. M. & Lettinga, G. (1998).
The anaerobic treatment of sewage in UASB and EGSB reactor: A review.
Bioresource Technol. 65, 175-190.
Spellman, F. R., (2003), In: Handbook of water and waste treatment plant operations,
lewis publisher, 365.
158
Subramanyam, R. & Mishra, I. M. (2007). Biodegradation of catechol (2-hydroxy
phenol) bearing wastewater in an UASB reactor. Chemosphere. 69, 816-824.
Tetra Pak Technical data manual, (2008). Hydrogen peroxide, Doc. No.OM-2771726-
0101. pp 8-9.
Yonar, T., Kestioglu, K. & Azbar, N. (2006). Treatability studies on domestic wastewater
using UV/H2O2 process, applied catalysis B: Environmental. 67, 223-228.
159
9 Chapter 9:
Major Findings and Future Recommendations
160
9.1 Major Findings
The present study on low-cost treatment of combined MWW containing food industry
effluents by UASB in combination with AOP as post treatment of UASB effluent can be
concluded as under:
161
regard, infrequent supply of waste H2O2 from industry can stop the treatment
process.
3. Some industries were selected to treat their wastewater. Carwash industry was
one of them whose effluent was not studied often. This wastewater contained
high content of oil 83 mg L-1 and COD >1000 mg L-1. Due to presence of oil it
was not feasible to treat directly with alum or H2O2. Therefore aeration was
added as pretreatment step to bring oil content ton the surface where it was
scraped out from aeration tank. Effluent from aeration tank was further treated
with alum in second step and H2O2 at third step. Treatment efficiency was 96%
oil, COD, turbidity and TDS were reduced upto 93%, 94% and 74%,
respectively. The present approach was proved cost effective and requires less
space without any pH control. Only costly factor was aeration to separate the
oil, other than aeration it can be more expensive to separate. Thus the treatment
process can be applied on pilot scale to further evalute its efficiency.
4. The present study compared the effectiveness of used and fresh H2O2 to treat
the domestic waste and to reduce the alum dose for chemical sedimentation. It
was observed that used waste 40% H2O2 was very effective and economical.
Fresh 35% H2O2 can be purchased Rs 40/L from the market but used waste
40% H2O2 can be obtained only from specific industries where it used for
disinfection. Using 40% waste H2O2 was found very effective to reduce COD,
turbidity and microbial load. An addition step was merged into H2O2 was UV
light to speed up the reaction. The proposed system was consists of two major
step where first sediments was settled down with alum and decant from first
step was used to treat with H2O2 and UV in the same tank. This proposed
system was effective to treat domestic wastewater but carwash and food
industry wastewater may require other treatment steps need to be added. The
combination of H2O2 with UV light was found very effective to decrease BOD,
COD, and turbidity and coliform bacteria in MWW. Waste H2O2 generated
from an industrial process of disinfection was found more effective in the
treatment of domestic wastewater than fresh 35% H2O2. The waste H2O2 can
162
be applied in combinations with UV light to treat domestic wastewater
effectively.
5. Up-flow anaerobic sludge blanket (UASB) reactor was used to treat mixed
MWW at hydraulic retention time 24-48 hrs and at an average temperature 25-
34ºC. The aim was to test two stage treatment concept for low cost MWW
treatment as UAB in first stage and waste H2O2 40% 2 ml L-1 of UAB effluent
at second stage. Moreover, the effect of micronutrients on the treatability of
UAB was also investigated. After start up with glucose for first 15days (first
stage), the reactor was fed with macro and micronutrients (SNI) for 45 days
(second stage). The maximum substrate removal rate was same 0.07 d-1 for
both glucose and SNI. Removal efficiency of total suspended solids (TSS),
chemical oxygen demand (COD), total nitrogen (TN), Ortho-P and Turbidity as
73%, 99%, 84%, 19% and 67%. Waste H2O2 was found successful in NH4+
removal during post treatment where 80% nitrogen was removed. Low cost
integrated treatment using UAB and H2O2 was found an excellent novel
treatment choice for mixed MWW in developing countries.
163
9.2 Future Recommendations
The present study of removal of COD ammonium and SS has proven to be very
promising for practical implementation in industry as well as for MWW treatment. It can
be more attractive when using waste from one industry to treat other industry waste.
Following recommendations should be considered for future work on UASB treatment in
combination with 40% waste H2O2.
1. Same type of reactor needs to acclimiate with high COD load such as 25000 mg
L-1 because some food industries espacially confectionary discharge at >4500 mg
L-1 with recycling. Handling such high load COD effluent could also pass through
increased sludge bed hight to avoid recylcing.
4. Different HRT still need to be investigated thoroughly. The treatment under very
HRT will be highly desirable to apply high organic loading. Using same sludge
collected from septic can be used to study extremely low HRT when treating
municipal and confectionary wastewater.
5. Post treatment with waste 40% H2O2 was used to treat UASB effluent for
municipal and confenctionary wastewater. There are still need to explore the
mechanism of nitrogen and phosphate removal during post treatment advanced
oxidation processes.
164
Curriculum Vitae
Name: Zulfiqar Ahmad Bhatti
Correspondence
address:
Environmental Sciences Department,
COMSATS Institute of Information Technology,
Tobe Camp Abbottabad. 22060.
Emails: zabhatti@ciit.net.pk
bhattizulfqar@yahoo.com
165
Jamil Khan, Rehana Rashid, Naim Rashid, Zulfiqar Ahmed Bhatti, Nadeem
Bukhari, Muhammad Aurangzaib Khan and Qaisar Mahmood., (2010),
“Assessment of Selected Organotin Complexes Against Plnat Pathogen Fungi”
sarhad J Agric., 26(1): 65-68.
Amir Haider Malik, Zahid Mahmood Khan, Qaisar Mahmood, Sadia Nasreen,
Zulfiqar Ahmad Bhatti; (2009), Perspective of low cost arsenic remediation of
drinking water in Pakistan and other countries, Journal of Hazardous Material,
(168) 1-12.
Sajid Hussain Shah., Donglei Wou, Qaisar Mahmood, Zulfiqar Ahmad Bhatti,
(2010), Low temperature conversion of plastic waste into light hydrocarbon,
Journal of Hazardous Material,179: 15-20.
Farhana Maqbool, Zulfiqar Ahmad Bhatti, Amir Haider Malik, Arshad Pervez
and Qaisar Mahmood, (2011), Effect of Landfill Leachate on the Water Quality of
the Salhad Stream in Abbottabad, Pakistan, Int. J. Environ. Res, V. 5(2):491-500
(ISI, IF=0.737).
166
Salhad Stream South Abbottabad, North Pakistan, 24th International Conference
on Solid Waste Technology and Management held in Philadelphia, PA, U.S.A. on
March 15-18, 2009.
Zulfiqar Ahmad Bhatti, Zahid Mahmood Khan, (2007); Fatty Acids Changes in
Endive Roots (Cichorium intybus) During Chilling Environment, ESDev- 2007,
613-622.
Zufliqar Ahmad Bhatti, Iftikhar Ahmad Raja, (2007), Particle Settling in
Continuous Flow Primary Sedimentation Tank Designed for Laboratory Scale
Municipal Wastewater Treatment, ESDev 2007, 860-869.
Zulfiqar Ahmad Bhatti, Iftikhar Ahmad Raja, (2005), Emission of VOC from
Fat Rendering Plant, ESDev-2005
Zulfiqar Ahmad Bhatti, Iftikhar Ahmad Raja, (2005), Water Purification Using
Micron Filtration and Ozonation for Ground Water, ESDev-2005, 1837-1866.
Saleem Farooq Shaukat, Zulfiqar Ahmad Bhatti, (2005), Removal of Chromium
from Industrial Effluents by Sono-Electrolysis Process, ESDev-2005, 827- 832.
167