Вы находитесь на странице: 1из 41



Submitted in partial fulfilment of the
Requirement for the award of the degree
(With specialization in Industrial Pollution Abatement)
Submitted by
Pushpraj Choudhary
Enrolment No. 16515011
Under the guidance of
Prof. B. Prasad



I hereby declare that the work which is being presented by me in this dissertation report entitled
Treatment of Pharmaceutical Wastewater by Fenton and Coagulation Processes submitted
in partial fulfillment of the requirement for the award of the degree of Master of Technology in
Chemical Engineering with specialization in Industrial Pollution Abatement and submitted to the
Department of Chemical Engineering, Indian Institute of Technology, Roorkee, is an authentic
record of the work carried out by me during the period October 2016 to November 2017, under
the guidance of Dr. B. Prasad, Professor, Chemical Engineering Department, Indian institute of
Technology, Roorkee.

Enrollment No.-16515011

This is to certify that the above statement made by the candidate is correct to the best of my

Dr. B. Prasad
Department of Chemical Engineering
Indian Institute of Technology Roorkee
Roorkee -247667, India


I am greatly indebted to my guide Prof. B. PRASAD, Department of Chemical Engineering,

Indian Institute of Technology Roorkee, Roorkee for his kind support and guidance during the
entire course of this work. His cooperation and in depth knowledge have made my work
I am also thankful to Prof. C. B. MAJUMDAR, Head of Department of Chemical
Engineering and other staff members for their instant help in all kinds of work.
I would like to thank my friends for their continuous support and enthusiastic help.
Last but not least, it is owed to the blessings of my parents and God that I have come up with
this work in due time.

Enrollment No.-6515011
M.Tech (IPA) IInd Year


Item description Page No.




a) Research Gap 13

b) Objective 14

a) General 15

b) Materials 15
c) Methods 15

a) General 19

b) Coagulation 19



Figures Name Page No

Figure 4.1 COD removal by coagulants at various pH 20

Figure 4.2 COD removal by Aluminium Sulphate coagulant at Different Dose 22

Figure 4.3 COD removal by ferric chloride coagulant at Different Dose 23

Figure 4.4 COD removal for Aluminium Sulphate (Al2(SO4)3.16H2O) with 25

time and different coagulant dose at a fix pH for (a) at pH=9, (b)
pH=7, (c) pH=4

Figure 4.5 COD removal for Ferric Chloride (FeCl3) with time and different 26
coagulant dose at a fix pH for (a) at pH=9, (b) pH=7, (c) pH=4


Tables Name Page No

Table 1.1 Pharmaceutical waste parameter and their standards 4

Table 1.2 Characterization of herbal pharmaceutical wastewater 5

Table 2.1 Pharmaceutical Wastewater Treatment Technology 11

Table 4.1 Characteristics of Pharmaceutical industrial wastewater 19

Table 4.2 Optimization of coagulant dose using Aluminium Sulphate at 21

different pH value

Table 4.3 Optimization of coagulant dose using Ferric Chloride at 22

different pH value


COD – Chemical oxygen demand

TOC– Total organic carbon
TDS – Total dissolved solids
TSS – Total suspended solids
TS – Total solids

Chapter 1

The Indian pharmaceutical industry is in the front rank of India’s science-based industries in
now days with wide ranging capabilities in the complex field of drug manufacture and
technology. Pharmaceutical waste products are among the most complex and toxic industrial
wastes. The pharmaceutical industry often generates moderately to-highly toxic wastewater with
seasonal and operational factors affecting the quality and quantity of the effluents. Bulk
pharmaceuticals are manufactured using a variety of processes including chemical synthesis,
fermentation, extraction and other complex methods (Elmolla et al., 2012).Generally, only a
fraction of the amount of antibiotics is transformed in the body and the rest are excreted in their
native form or as metabolites (Elmolla and Chaudhuri, 2011). A variety of pharmaceuticals have
been reported to be present in the effluent of sewage treatment plants (STPs), indicating their
poor biodegradability in municipal sewage and STPs (Kulik et al., 2008). They may enter
aquatic environments (surface water and groundwater) or soil and can lead to the development of
resistance of microbial pathogens to antibiotics.
The presence of Pharmaceuticals and Personal Care Products (PPCPs) was first identified in
surface and wastewaters in the United States and Europe in 1960s (Stumm-Zollinger and Fair,
1965). Concerns about their potential risk was raised in 1999 (Daughton and Ternes, 1999) with
the issue attracting considerable interest after the presence of pharmaceuticals in river water was
linked to feminisation of fish living downstream of Waste Water Treatment Plant (WWTP)
outfalls (Larsson et al., 1999). Furthermore, a link between a non-steroidal anti-inflammatory
drug, diclofenac and the renal failure of vultures contributing to the > 95 % decline in its
population in the Indian subcontinent since the 1990’s has been reported (Oaks et al., 2004).
Public awareness were raised after a study showed that organic wastewater contaminants,
including PPCPs, were present in 80 % of 139 U.S. streams (Kolpin et al., 2002). Although the
concentration levels of PPCPs found in the environment are at trace concentrations, their
chemical persistence, microbial resistance and synergistic effects are still unknown (Ankley et
al., 2007;Madukasi et al., 2010), which is a cause for concern. Moreover, low concentrations can
elicit adverse effects on aquatic life (Miege et al., 2008; 2009).Pharmaceuticals enter the
environment from a myriad of scattered points. The main sources of contamination include
pharmaceutical production plants, WWTPs, hospitals, landfills and even graveyards (Khetan and

Collins, 2007; Lillenberg et al., 2010). The most investigated route of entry of pharmaceuticals
into the environment is that from municipal WWTPs. Human excretion of unchanged or slightly
transformed Active pharmaceutical ingredients (APIs) conjugated to polar molecules such as
glucoronide enters the WWTP where these conjugates may then be cleaved, releasing the
original API into the environment (Heberer, 2002). Activated sludge WWTPs has received
particular attention (Jones et al., 2007; Watkinson et al., 2007). A limited number of studies also
found pharmaceuticals in drinking water (Webb et al., 2003) and hospital wastewater (Suarez et
al., 2009). Monitoring of APIs being released from pharmaceutical production facilities is not
routine and the importance of such releases has not yet been established (Larsson and Fick,
2009). Furthermore, pharmaceutical industry wastewaters may contain organic solvents,
catalysts, additants, reactants, intermediates, raw materials and APIs (Sreekanth et al., 2009),
which makes them difficult to treat. The presence of toxic or recalcitrant substances in such
wastewater results in lower Chemical oxygen demand (COD) removal efficiencies (Chelliapan et
al., 2006). It has been estimated that up to half of the pharmaceutical wastewater produced
worldwide is released without any treatment (Enick and Moore, 2007). While some attention has
been focused on Endocrine disrupting chemicals (EDCs) the removal of other specific APIs is
largely ignored. Biological treatment of wastewater is the most common and economical
wastewater treatment method (Kulik et al., 2008). However, biological methods have shown to
be insufficient for the removal of all potentially hazardous constituents of the wastewater (Clara
et al., 2005; Joss et al., 2005; Suman Raj and Anjaneyulu, 2005; Giri et al, 2008; 2010).
Recently, Membrane bioreactor (MBR) technology, ozonation and advanced oxidation processes
(AOPs) have shown varying degrees of efficiency for the treatment of pharmaceutical
wastewaters (Andreozzi et al., 2005; Doll and Frimmel, 2005a, Andreozzi et al., 2006).As the
awareness of the inefficiencies of the individual treatment technologies for the removal of
hazardous substances in pharmaceutical wastewater is increasing, the integration and
combination of treatment technologies may provide a more effective, albeit expensive solution in
the future. This review aims to provide an overview of the current knowledge regarding the
range of treatment methods available for PPCP removal from industrial wastewaters in order to
get baseline knowledge of the effectiveness of the various treatment options. This knowledge
could help pharmaceutical production facilities to be prepared to take preventative measures
before required to do so by legislation.

Pharmaceutical industry produces a wide variety of products. It uses both inorganics and
organics as raw materials; the latter is either of synthetic or of plant and animal origin.
Generally, most of these wastes are toxic to biological life and are usually characterized by high
BOD, chemical oxygen demand (COD) values and a low BOD/COD ratio, which is the main
problem causing the failure of biological treatment. The existence of such compounds (e.g.,
pharmaceuticals and hormonally active substances) in the aquatic environment and their possible
effects on living organisms are giving rise to growing concern. In fact, more than 50
pharmaceutical compounds have been detected during the last years in different aquatic
environmental samples, due to the continuous improvement of the analytical techniques. Many
of these samples have been collected from wastewater, and also from surface or ground waters.
These compounds originated either from domestic sewage or from hospital or industrial
discharges and enter municipal sewage treatment plants. Previous studies show that the common
conventional methods of treatment (i.e., biological, physical, and chemical methods) were
applied for the treatment of the effluents. Limited success has been achieved because these
processes are less effective, or even ineffective against the very stable refractory and toxic com-
pounds. Another main drawback of these processes is that they are associated with the
generation of large amount of sludge, which requires thermal destruction before final disposal.
Recently, much attention has been paid to separate the source of the refractory or toxic effluent
and treat it by advanced oxidation processes (AOPs) using homogeneous or heterogeneous
catalysts. Fenton system Fen+/H2O2 is one of the most interesting promising oxidative
techniques for the abatement of refractory and/or toxic organic pollutants in water and
wastewater. The high removal efficiencies of this technique can be explained by the formation of
strong hydroxyl radical (HO•) and oxidation of Fe2+ to Fe3+. Both Fe2+ and Fe3+ ions are
coagulants, so the Fenton process can, therefore, have dual function, oxidation and coagulation
in the treatment processes. Moreover, iron is a highly abundant, non-toxic element. In addition
hydrogen peroxide is easy to handle environmentally. Therefore, the aim of the present study is
to investigate the efficiency of the proposed treatment processes for the removal of the refractory
organic compounds from pharmaceutical industrial wastewater before being discharged into
sewerage system.
Assessment and characterization of wastewater is important to evaluate the quality of
wastewater. In India, the Central Pollution Control Board (CPCB) provides standards with their
limiting concentrations for discharge of environmental pollutants from the pharmaceutical
(manufacturing and formulation) industry (Table 1.1)
Table 1.1: Pharmaceutical waste parameter and their standards

Parameter Parameter in mg/l except pH

(effluent standards) (effluent standards)
Compulsory parameters
pH 6.0-8.5
Oil and grease 10
BOD (3 days at 27 _oC) 100a
COD 250a
Total suspended solids (TSS) 100
Total dissolved solids (TDS)** -
Bioassay test 90 % survival after 96 h
in 100 % effluentb
Additional parameter*
Mercury 0.01
Arsenic 0.2
Chromium (hexavalent) 0.1
Lead 0.1
Cyanide 0.1
Phenolics 1.0
Sulphides 2.0
Phosphate 5.0

* Parameters listed as ‘‘Additional parameters’’ shall be prescribed

depending upon the process and product
** Limits for total dissolved solids in effluent shall be prescribed by
the concerned pollution control board/pollution control committee
depending upon the recipient water body
a The BOD and COD limits shall be 30 mg/l and 250 mg/l respectively,
if treated effluent is discharged directly into a fresh water body,
i.e. stream, canal, river or lake
b The Bioassay Test shall be conducted as per IS: 6582-1971

Herbal medicines are being used by about 80% of the world population primarily in the
developing countries. Herbal medicines include herbs, herbal materials, herbal preparations and
finished herbal products that contain as active ingredients from plants or other plant materials.
Of all the sciences, India possesses the longest and most glorious tradition in the field of herbal
medicine. Herbal pharmaceutical industries generate moderately concentrated wastewater in
huge volumes in terms of COD, BOD, and SS. Characterization of wastewater from herbal

pharmaceutical industry is shown (Table 1.2), reveals that the pollution load of the effluent in
terms of COD, BOD and SS is in the range of 21960 -26000 mg/L, 11200 -15660 mg/L and
5460 -7370 mg/L respectively (Vanerkar et al., 2013).

Table 1.2: Characterization of herbal pharmaceutical wastewater (Vanerkar et al., 2013)

Parameters Raw wastewater

pH 3.9 - 4.0
Colour (Visual) Dark yellow
Total Acidity 3000
Total Suspended Solids 5460 – 7370
Total Dissolved Solids 2564 – 3660
Total Solids 8024 – 11030
Chemical Oxygen Demand (COD) 21960 – 26000
Biological Oxygen Demand (BOD, 5day - 20°C) 11200 – 15660
Sulfide as (S -2) 42 – 54
Sulphates as (SO4-2) 82 – 88
Total Phosphates as (PO4-2) 260 – 280
Total Nitrogen as N 389 – 498
Oil and Grease 140 – 182
Sodium as Na+ 155 – 266
Potassium as K+ 128 – 140
Heavy Metals
Iron 65.6 - 65.7
Copper 0.649 - 1.67
Manganese 6.41 - 8.47
Nickel 0.892 - 2.35
Zinc 0.583 - 0.608
Chromium 0.057-1.11
Lead 0.559 - 6.53
Cadmium 0.036 - 0.484
Selenium 0.428 - 0.666
Arsenic 0.0049 - 0.0076

*All values are expressed in mg/L except pH and colour.

Chapter 2

Wastewater from pharmaceutical manufacturing plants is more problematic due to number of

different treatment method. Following are few research studies based on treatment methods for
pharmaceutical wastewater.

Aswini et al. (2014) highlighted the electrocoagulation is a treatment process that is capable of
being an effective treatment process as conventional methods such as chemical coagulation. It
observed trends over the last years, it has been noted that electro coagulation is capable of
having high removal efficiencies of colour, chemical oxygen demand (COD), bio chemical
oxygen demand (BOD), and achieving a more efficient treatment processes quicker than
traditional coagulation and inexpensive than other methods of treatment such as ultraviolet (UV)
or ozone.
Ashfaq and Khatoon (2014) concluded that there are various conventional treatment processes
available for treating pharmaceuticals in waste water. In addition there are a number of
promising new treatments including AOPs such as oxidation, ozonation, perozonation, direct
photolysis, TiO2 photo catalysis, solar photo catalysis, and Fenton reactions ultrasonic
irradiation. These significantly enhance the removal rate of pharmaceuticals from wastewaters.
Comparisons among these technologies are problematic since most researchers used synthetic
water rather than actual wastewater samples.
Ctia et al. (2014) reported the effect of the temperature used in the decontamination step was
also tested. Temperatures of 30◦C and room temperature 20 ◦C were used. The results proved
that the temperature affected positively the degradation rate, higher conversion values were
obtained when 30◦C were used.
Gome and Upadhyay (2013) their study deals with the treatment of pharmaceutical industry
wastewater by ozone. An attempt has been made to assess the biodegradability of the selected
pharmaceutical wastewater sample. It was found that higher treatment time favored the
enhancement of biodegradability of selected sample. It can be concluded that ozone treatment
can improve biodegradability of pharmaceutical wastewater.
Tiwari and Upadhyay (2013) conclude that Fenton’s oxidation enhances the biodegradability
of Aqueous Mother Liquor Effluent (AMLE) which further treated by coagulation and Activated
Sludge Treatment Process (ASP). The biodegradable organic matter present in waste water

removes in ASP by biosorption, biooxidation including nitrification and bioflocculation but due
to the high organic load, biorecalcitrant compound, surfactants or biotoxicity in the Activated
Sludge Treatment Process (ASP) did not perform effective treatment as a result we obtained
biologically treated effluent with high COD, TSS and TDS value, loss of biomass in treated
effluent, biomass rupturing in aeration tank and poor settling of biomass in secondary clarifier.
Therefore to deactivate the property and to prevent shock loading and to improve the
biodegradability for ASP the Advanced Oxidation played very important role.
Nese et al. (2013) showed the reaction rates of Fenton oxidation of the dyes were rather slow in
alkaline medium while they were fast in acidic medium.
Lalwani and Devadasan (2013) their experiments conclude that conventional biological
treatment of the common effluent treatment plant (CETP) should be replaced with physico-
chemical process like advanced oxidation process. The study showed that among the two
oxidants Sodium Hypochlorite and Fenton’s reagent, the latter is the most efficient as the
maximum COD and BOD reduction was observed for this oxidant.
Hannah et al. (2012) stated that the treatment of the antibiotic wastewater with various different
AOP (advance oxidation process) combinations proved to be successful in the removal of COD
and TOC. An increase in sulphate concentrations was also witnessed. H2O2 concentrations were
experimented with for the O3/ H2O2 combined AOP. Although O3 is able to produce H2O2 alone
by the breakdown of organic matter, it was concluded that the addition of H2O2 artificially to the
system greatly accelerated the formation of the hydroxyl radicals necessary for the efficacy of
the system and allowed shorter contact times.
Renge et al. (2012) concluded that there are a number of promising new treatments including
AOP’s such as oxidation, ozonation, direct photolysis, TiO2 photo catalysis, solar photo
catalysis, Fenton reactions and ultrasonic irradiation. These significantly enhance the removal
rate of micro pollutant from wastewaters. Comparisons among these technologies are
problematic since most researchers used synthetic water rather than actual wastewater samples.
Research is required in this area to improve treatment efficiencies, identify degradation
compounds and to determine the cost and feasibility of full-scale applications. There is also
interest in coupling AOPs with more conventional treatments such as activated carbon. Finally,
the problem of micro pollutant in wastewaters cannot be solved even if it is considerably
alleviated - merely by adopting end of pipe measures. At-source measures like replacement of
critical chemicals, reduction in raw material consumption should continue to be pursued as the
top priority.
Libing et al. (2012) found that the oxidation potential of hydroxyl radicals decreased with
increasing pH. Removal of COD and phenol compounds depended on the initial solution pH.
Hussaina et al. (2011) compared the advanced oxidation processes (AOPs) utilizing H2O2/Fe+2,
Fenton reactions were investigated inlab-scale experiments for the COD degradation of different
waste water streams of Active Pharmaceutical Intermediates -ISMN (Isosorbide 5- Mononitrate).
The experimental results showed that the Fenton process using H2O2/Fe+2 was the most effective
pre-treatment process for waste water streams before activated sludge process. With Fenton
processes, COD reduction of wastewater can be achieved successfully. It is suggested that
Fenton processes are viable techniques for the degradation of Active Pharmaceutical
Intermediates- ISMN (Isosorbide5- Mononitrate) waste water stream with relatively low toxicity
of the by-products in the effluent which can be easily biodegradable in the activated sludge
process, and other less degraded streams with high total dissolved solids can be taken to multiple
effect evaporator or reverse osmosis.
Karthikeyan et al. (2011) studied that the percentage removal of COD increased linearly up to
4 h and was followed by a non-linear increase up to 50% in 6 h.
Soraya et al. (2010) studied that the influence of agitation rate during oxidation of leachate was
studied varying the magnetic stirrer rate. The results showed varying the agitation speed had a
marked effect on the COD and color removal efficiencies. High agitation rates led to more rapid
and high efficient process. Increasing the rotation speed had increased the COD and color
removal; however as the rotation speed was more than 400 rpm, the reduction in the COD and
color was not recorded.
Soraya et al. (2010) evaluated a set of experiments and find that the amount of Fenton’s reagent
necessary for an effective treatment must be determined. The steady state concentration of
hydroxyl radicals depends on the absolute amounts of H2O2 and Fe2+. Therefore, in order to
assess the relationship between the COD removal and reagents dosage, fixing the H2O2/ Fe2+
molar ratio at 1:3 as optimum dosages and treating the leachate by varying the amounts of both
reagents. The COD and color removal efficiencies increased with increasing amount of Fenton
reagent concentration, up to the optimum dosages (H2O2/ Fe2+ = 0.03 mole/0.01 mole). Higher
dosages resulted in lowered COD and color removals. This was explained considering that the
hydroxyl radical may be scavenged by the reaction with excess Fe2+ and H2O2. the best oxidation
efficiency was achieved when neither H2O2 nor Fe2+ was overdosed, so that the maximum
amount of OH radicals was available for the oxidation of organic compounds.
Soraya et al. (2010) studied that the reaction temperature of 30◦C was considered appropriate
and all experiments were carried out at room temperature, for practical and economic reasons.
Rodrigues et al. (2009) reported that the rate of degradation increased with an increase in the
concentration of ferrous ion.
Tekin et al. (2006) showed that the effects of reaction temperature on COD and color removals
were evaluated over the range of 30–60◦C. no significant differences were observed in the
treatment efficiencies for the 30 to 50◦C tested temperatures; beyond that COD and color
removal efficiencies decreased slightly. Temperatures higher than 50◦C may negatively affect
COD removal because the flocs formed may be destabilized at high temperatures. the
temperature of wastewater almost does not affected the efficiency of COD removal in Fenton’s
Ried et al. (2006) stated that advanced COD reduction is required and an existing biological
treatment does not achieve the limits given by existing or new regulations, several options are
available to achieve lower COD levels. During ozonation of waste waters the generation of
hydroxyl radicals takes place without using additional arrangements. A certain balance between
direct ozone reactions and radical reactions will appear. Whether an additional enhancement by
UV or H2O2 is actually promising, has to be evaluated separately. And also stated that the best
available advanced oxidation process (AOP) depends on the wastewater conditions and the
treatment goals by taking also the actual cost into account. As advanced treatment of municipal
and industrial waste waters the use of ozone and probably AOP (Advanced oxidation process)
enables to meet future water clarification and recycling standards in an economic feasible way.
Especially the existing regulations for COD and the possible future regulations for different kind
of persistent substances, e.g. industrial chemicals, ozone /H2O2.
Gupta and Gupta (2006) studied and highlighted on treatability study of almost all kinds of
waste streams that indicated the waste is biologically treatable. Hence, a combination of
physical, chemical, and biological processes seems to be feasible for the treatment of
pharmaceutical wastewater. A two-stage biological system or a combination of aerobic and
anaerobic processes proved effective for some pharmaceutical wastewater. Keeping in mind the
varying characteristics of pharmaceutical wastewater, the shock loading capacity of the
treatment units must also be given much attention in identifying and evaluating the technical
feasibility of the processes. After identifying the technical feasibility of the processes, the final
selection should be made based on economic analysis.
Sebastián et al. (2003) express the operational parameters influencing the Fenton’s reaction in
the pre-oxidation of an extremely polluted wastewater have been studied by means of an
experimental design, in which the factors considered were temperature, ferrous ion and hydrogen
peroxide concentration. The temperature only showed a mild positive effect on COD removal.
Consequently, temperature should not be considered in the optimization of the Fenton’s reaction
for this wastewater. This finding is of special interest in the industrial application of Fenton’s
reagent, because it permits a significant COD reduction in a very short period of time. The
results here presented can be considered as an effective pre-treatment of this type of
wastewaters, when direct biological treatments are not possible.
Kang et al. (2000) studied that an enormous increase in the ferrous ions leaded to an increase in
the unutilized quantity of iron salts, which contributed in an increase of the total dissolved solids
content of the effluent stream and this was not permitted.

Table 2.1: Pharmaceutical wastewater treatment technology

S.No. Treatment Parameter Studied Remark Author


Photocatalysis pH(8.2); phenol( 380 Addition of H2O2 to the

1 Kumar and
(TiO2) + H2O2 mg/L); chlorides(182 system increases
mg/L); sulphates(160 Kanmani (2010)
in a single degradation rate from 75
baffled mg/L), COD(1082 to 95%.Also, phenol
reactor for the mg/L);BOD(170 mg/L); removal rate enhanced
process. BOD:COD(0.15) from 40% to 45%. The
combination of H2O2 to
the photo catalytic
System enhanced the
effluent removal rate.

Photocatalysis penicillin formulation 10−20% COD removal Arslan-alaton and

(Fenton + effluent: COD(1395 after 60 min and Poor Dogruel (2004)
photo-Fenton + mg/L); TOC(920 mg/L) improvement in
O3) biodegradability

Ozonation penicillin formulation Preozonation enhanced

3 (pretreatment) + effluent: filtered COD(830 the biodegradability of the Alaton et al.
biological mg/L); soluble COD(615 effluent. Efficiency of the (2004)
activated mg/L); pH(6.9); process for COD, around
sludge reactor amoxicillin trihydrate; 90% removal with the
combination in lactamase inhibitor; organic content. The
series potassium clavulanate combination of
preozonation and
biodegradation is the best
option for pharma
Antibiotic formulation
waste was made Preozonation helps to
Chemical synthetically by reduce the COD level to a
4 oxidation characterizing the actual great extent and H2O2
ozonation and industrial waste: antibiotic enhances the process to Balcıoglu and
ozonation I (ceftriaxone sodium, the maximum. Also, the Otker (2003)
coupled with cephalosporine group); biodegradability
treatment with human antibiotic II characteristic of the waste
hydrogen (penicillin VK and also increases. Thus,
peroxide penicillin group; contain ozonation can be
only active successfully applied as a
substances);veterinary pretreatment.
antibiotic nrofloxacin,
quinolone group are prime
constituents. COD up to
1400 mg/L

COD elimination was
Solar photo- main effluent in water is 95%, of which 33% was
Fenton and 45 mg/L nalidixic acid accomplished by the solar Sirtori et al.
biological with 775 mg of dissolved photo-Fenton treatment (2009)
treatment organic carbon/L: COD, and 62% by the biological
3420 mg/L; pH, 3.98 treatment. Wastewater can
be successfully treated by
photo-Fenton treatment
with peroxide usage and
low toxicity removal

6 Fenton-like Azithromycin antibiotic COD removal by the

(Fe/H2O2) synthetic wastewater with Fenton-like process is Yazdanbakhsh et
system in COD of solution is 200 increase with increase pH al. (2014)
combination mg/L,pH value change value and also increase
with coagulation from 3 to 10 with H2O2 concentration.
Increase in Coagulant
dose COD removal also

Research gaps

Following research gaps are found during literature review:

 Most of the studies were done on the synthetic pharmaceutical wastewater.
 Only a few studies are done on integration of Fenton and coagulation process
 No study was reported on comparing of Fenton and coagulation process for treatment of
pharmaceutical wastewater.
 Disposal aspects of the spent sludge were not reported.
 Thermal analysis of sludge generated during coagulation was lacking in all studies.
 In the most of the fate studies of pharmaceuticals in Indian WTPs involve grab samples
that may result into the over or under-estimation of actual mass loads and environmental
emission of drugs, they only focused on COD, BOD, TSS, TDS, etc.


The major aims and objectives of the present research work are as follows:
1. To characterize the industrial pharmaceutical wastewater (COD, pH, TDS, TOC, TSS,
anions, cations etc.)
2. Use of Fenton and Coagulation techniques for treatment of pharmaceutical wastewater
A. Fenton treatment
a) Study the effect of Fenton’s reagent (H2O2/Fe+2) on COD removals
b) Parameter study (dosage, time, pH, etc.)
B. Coagulation treatment
a) Selection of suitable coagulants
b) Parametric study viz. pH, temperature, dosage, time, etc on removal efficiency of
3. Optimization of process through Response Surface Methodology (RSM).
4. Comparative Study between Fenton and Coagulation processes.
5. Study of degradation kinetics of both processes at optimum condition.
6. Study of sludge generated at optimum operating conditions.
7. Economic analysis of both the processes.

Chapter 3



Having fixed the aims and objectives on the basis of literature review, an extensive
research program on the treatment of Pharmaceutical wastewater through coagulation was
carried out. This chapter deals with the materials and methods of analysis, and the experimental
procedures adopted to collect the experimental data.


3.2.1. Source of wastewater

The wastewater was collected from the Pharmaceutical industry, situated in Jaipur
(Rajasthan) and they manufacture medicines, tablets, syrups, capsules. The wastewater was
stored at 4 °C in a refrigerator in the laboratory and was used subsequently without any dilution
in the experiments.

3.2.2. Coagulation study

The inorganic chemical coagulants, viz. analytical grade ferric chloride and aluminium
Sulphate were procured from M/S, RFCL, New Delhi and used as organic coagulants. Cationic
polyacrylamide (C-PAA) (HiMedia, Mumbai) was used in settling studies.

3.3.1 Experimentation Coagulation experiments:
Coagulation studies were performed using a jar test apparatus. The optimum
concentration of various coagulants with respect to removal of COD was determined through
extensive jar test studies. The wastewater was treated in batch mode in 100 ml glass jar at
various coagulant dosages and analyzed. The experimental procedure consisted of three phases:
A period of 1 min was allowed for the flash mixing of the coagulant, at 250 rpm. It was followed
by a further slow mixing at 50 rpm for 30 min and in the final stage the flocs were allowed to
settle for 30 min. The supernatant obtained after 30 min of settling was subjected to COD
analysis. Equal volume glass beakers were used to examine different dosage of coagulants in the

range of 300-1500 mg/l. The samples taken in the beakers were thoroughly shaken for the
mixing of settled solids and appropriate volume of the same was then transferred to the
corresponding jar test beakers. For coagulation experiments, pH was varied from 4 to 9 by
addition of 1 N H2SO4 for acidic region and 1 N NaOH for alkaline range. Experimental Setup

Coagulation treatment setup for wastewater comprises of a 250 ml lab-scale glass batch
reactor with circular cross section. Entire experimental runs were conducted at 25±5oC
temperature and at 250 rpm.

Figure 3.1 Schematic representation of experimental setup

3.3.2 Analytical Methods

The wastewater was analyzed for various physico-chemical parameters such as pH,
COD, total solids (TS), Total Organic Carbon (TOC), Total Suspended Solids (TSS),
Conductivity, Colour, Turbidity, Anions and Cations. The pollution of the Pharmaceutical waste
water was measured in terms of Chemical Oxygen Demand (COD). The COD value was analyze
with a COD analyzer (Aqualytic, Germany).

16 Analysis of raw and treated effluent Chemical Oxygen Demand (COD)
To examine the COD of the effluent, AQUALYTIC COD Reactor and ET 100 (a direct
reading spectrophotometer) were used. The oxidant measured is the dichromate ion (Cr2O7 -2)
reduced to the chromic ion (Cr3+). The dichromate ions are strongly absorbed at 400 nm but
nearly zero at 600 nm. The chromic ion has its strongest absorbance at 400 nm but nearly zero at
600 nm. The chromic ion has its strongest absorbance at 600 nm thus allowing measurement of
the reduction from the dichromate to the chromic ion. Pre-Pared solutions of the COD solution
were obtained from AQUALYTIC Company (Germany).
The COD reactor was preheated to 150 °C. The sample vials were prepared as the reactor
was getting heated. The COD digestion reagent vials used came in three concentrations. The first
set read 0-150 mg/ L, second 0-1500 mg/ L and the third set read 0-15000 mg/ L. To prepare the
0-150 and 0-1500 mg/L vials 2 ml of each sample was added to its own vial. The 0-15000 mg/L
vials only required 0.2ml because each vial contained a built in dilution factor of ten. The vials
containing the samples were sealed tightly and shaken. They were then put into the heated COD
reactor and allowed to digest for two hours. At the end of two hours, the vials were cooled and
read in the spectrophotometer. The spectrophotometer – stored programs were used to read the
vials. Wavelength 430 nm was use to read low range COD and for the high rage COD, a
wavelength of 605 nm is used. These programs take the amount of absorption and insert it into
an internal calculation to determine mg/ L of COD. The spectrophotometer was first zeroed with
a blank that contained de-ionized water with the digestion solution. Each sample’s exterior was
wiped clean and read with results recorded in mg/ L COD.


Potassium dichromate reagent (Digestion Solution): First weight potassium dichromate

(K2Cr2O7) accurately 10.216 g which dried previously at 105°C for 2 hours in an oven and put it
into a beaker. After it, mercuric sulphate was taken 33.3 g accurately and put it also in same
beaker. Concentrated sulphuric acid (H2SO4) was taken carefully of 167mL by dried and clean
measuring cylinder and put down it into the same beaker and weight until dissolve all things in
beaker at room temperature, when all material was dissolved make this solution up to 1000 mL
with the distilled water by using a funnel. Keep this solution in a glass bottle of 1 L capacity and
use it for COD determination of the samples.

Sulphuric acid reagent (Catalyst Solution): Solution for catalysed the samples were prepared by
using silver sulphate and concentrated sulphuric acid. So, 5.5 g (per Kg of H2SO4) previously dried
silver sulphate crystal was put into a clean and dry beaker with capacity of 1 L. It was mixed with
concentrated sulphuric acid of 543 mL and grant to stand for one day (for completely dissolve of
silver sulphate crystals).


a. Treatment of sample with COD of > 50mg/L

b. Blend sample if suspended matter is present

c. Wash culture tubes and caps with 20% H2SO4 before first use

d. Refer the following to select analytical parameters for proper sample and reagent volume

e. Place sample in culture tube

f. Add digestion mixture

g. Carefully run sulphuric acid reagent down inside of vessel

h. Tightly cap the tubes. Invert several times for proper mixing

i. Place tubes in preheated reaction block digester

j. Reflux for 2h at 150°C behind a protective shield

k. Cool to room temperature

l. Measure the COD with the help of standard blank sample in COD COD analyzer


%COD Removal = ×100

Co=initial COD value (mg/l)

Cf= final COD value (mg/l)

Chapter 4



This chapter presents the results and discussion pertaining to the treatment of Pharmaceutical
wastewater through coagulation.
Wastewater was collected from the pharmaceutical industry for performing various studies.
These wastewaters were characterized for various parameters such as pH, COD, total solids
(TS), total solids (TS), Total Organic Carbon (TOC), Total Suspended Solids (TSS),
Conductivity, Colour, Turbidity, Anions and Cations. And all studies had done at room
4.2.1 Characteristics of Pharmaceutical industry wastewater

The characteristics of wastewater which was collected from a drug (medicines) manufacturing
plant as analyzed are presented in Table 5.1. The wastewater, comprising of both organics and
inorganics, is slightly basic in nature.

Table 4.1 Characteristics of Pharmaceutical industrial wastewater

Parameters Raw Wastewater

pH 8.05 ±0.5
COD 4100-4150 mg/L
TOC 1184 mg/L
Colour 2680 pt/Co
TDS 1005±5
Conductivity 2.5µS/cm
Turbidity 185NTU
Fluoride 4.990 mg/L
Chloride 130951.206 mg/L
Nitrite 460.094 mg/L
Bromide 2.265 mg/L
Nitrate 0.065 mg/L
Phosphate 8.776 mg/L
Sodium 9241.722 mg/L
Ammonium 1430.144 mg/L
Potassium 389.754 mg/L
Magnesium 158.163 mg/L

4.2.2 Effect of pH on percent removal COD by Aluminium Sulphate and Ferric Chloride
Figure 4.2 shows the effect of solution pH on COD removal by coagulants viz. ferric chloride,
aluminium sulphate. The organics generally get adsorbed on to pre-formed flocs of metal
hydroxides and thereafter get precipitated. The net result is the removal of dissolved organics
with different functional groups at different pH. The maximum COD removal may thus occur at
a pH where the combined effect of both the mechanisms is maximum. The optimum pH was 9
for ferric chloride with COD removal efficiency of 58.17% and for aluminium sulphate the
optimum pH was 7 with COD removal efficiency of 63.90%.

% Removal of COD

20 Aluminium Sulphate
Ferric Chloride
0 2 4 6 8 10

pH Value

Figure 4.1 Effect of pH on percent removal COD by Aluminium sulphate and Ferric
chloride coagulants

4.2.3 Determination of optimum dosage for COD removal

The optimal dosages of the coagulants were determined by varying the coagulant dose at the
optimal pH. The study range of the dosage was 300 - 1500 mg/ L. The optimum dosage for ferric
chloride was 900 mg/L. The optimum dosage for aluminium sulphate was obtained as 1200
mg/L. At optimum conditions of pH and coagulant dosage, the maximum COD removal
efficiency was 58.17% with ferric chloride. It may be attributed to the following reasons: (1) the
increase of adsorptive surface due to increase of ferric hydroxide precipitates, and (2) the
formation of flocs and acid anion complexes by electrostatic interaction. The complexes led to an
enhancement of removal of colloids. The maximum COD removal efficiency with aluminium
sulphate (1200 mg/L) was found 63.9% (Figure 4.2). When the dosage of ferric chloride was

increased beyond 900 mg/L, the removal efficiency decreased. With the addition of larger
dosage of the coagulant, the surface charge of the particles gets reversed due to continued
adsorption of mono and polynuclear hydrolysis species of ferric chloride. As the colloidal
particles become positively charged, they cannot be removed by per kinetic flocculation. COD
removal with coagulant dosage at different pH as shown below.

Table 4.2 Optimization of coagulant dosage using Aluminium Sulphate at different pH


% Removal of COD

Coagulant Dosage
(mg/L) pH=4 pH=7 pH=9
300 37.07 46.09 44.02

600 41.09 54.02 53.04

900 46.82 59.63 59.87

1200 49.02 63.9 61.46

1500 52.43 64.26 55.97

% Removal of COD


20 pH=9


0 200 400 600 800 1000 1200 1400 1600

Coagulant dosage (mg/L)

Figure 4.2 Percent COD removal by Al2(SO4)3.16H2O coagulant at Different Dose

Table 4.3 Optimization of coagulant dose using Ferric Chloride at different pH value

% Removal of COD
Coagulant dosage
(mg/L) pH=4 pH=7 pH=9
300 38.78 39.87 47.07

600 41.34 44.75 51.09

900 46.09 49.02 58.17

1200 51.09 55.12 53.65

1500 48.04 53.04 58.29


60 FeCl3
% Removal of COD

20 pH=9

0 200 400 600 800 1000 1200 1400 1600

Coagulant dosage (mg/L)

Figure 4.3 Percent COD removal by FeCl3 coagulant at Different Dose

4.2.4 Effect of contact time

Fig. 4.5 (a), (b), (c) and Fig. 4.6 (a), (b), (c) show the effect of contact time on percent removal
of COD removal. A fast uptake was seen during first 30 min to 40 min for both coagulants, and
approximately 56% of COD was removed at pH=7 using Aluminium Sulphate and 54% COD
was removed at pH=9 by Ferric Chloride. The maximum COD removal was found 63.90% with
aluminium sulphate coagulant and 58.17% with ferric chloride coagulants at 100 min. Beyond
this optimum contact time, COD removal was not increased.

For Aluminium Sulphate (Al2(SO4)3.16H2O)

60 pH=9
% Removal of COD


300 ppm
30 600ppm

0 20 40 60 80 100 120



60 pH=7
% Removal of COD

40 300 ppm
20 1200ppm
10 1500ppm

0 20 40 60 80 100 120



% Removal of COD

300 ppm
20 900ppm
0 20 40 60 80 100 120

Time (min)


Figure 4.4 COD removal for Al2(SO4)3.16H2O with time and different coagulant dose at a
fix pH for (a) at pH=9, (b) pH=7, (c) pH=4

For Ferric Chloride (FeCl3)

% Removal of COD

60 FeCl3
50 pH=9
40 300 ppm

0 20 40 60 80 100 120

Time (min)



% Removal of COD
300 ppm
20 900ppm
10 1200ppm
0 20 40 60 80 100 120

Time (min)


% Removal of COD

60 FeCl3
50 pH=9
40 300 ppm

0 20 40 60 80 100 120

Time (min)


Figure 4.5 COD removal for FeCl3 with time and different coagulant dose at a fix pH for
(a) at pH=9, (b) pH=7, (c) pH=4

Chapter 5



On the basis of the result and discussion presented heretofore for the treatment of
purified pharmaceutical wastewater by coagulation, following major conclusions can be drawn:

5.1.1 Coagulation

 Optimum pH for COD removal from Pharmaceutical wastewater by FeCl3 was found to
be 9 and for Aluminium Sulphate the optimum pH was 7.
 Optimum dosage for Ferric Chloride (FeCl3)and Aluminium Sulphate
(Al2(SO4)3.16H2O)was 900 mg/L and 1200 mg/L , respectively.
 COD removal by inorganic coagulant was due to charge neutralization.
 Maximum COD removal efficiency by Ferric Chloride (FeCl3)and Aluminium Sulphate
(Al2(SO4)3.16H2O) was 58.17% and 63.90% respectively.

Future Work

The following work is going to be done in future:

1. Fenton treatment
a) Study the effect of Fenton’s reagent (H2O2/Fe+2) on COD removals
b) Parameter study (dosage, time, pH, etc.)
2. Comparative Study between Fenton and Coagulation processes.
3. Optimization of process through Response Surface Methodology (RSM).
4. Study of degradation kinetics of both processes at optimum condition.
5. Study of sludge generated at optimum operating conditions.
6. Economic analysis of both the processes


Alaton IA, Dogruel S, Baykal E, Gerone G (2004) Combined chemical and biological
oxidation of penicillin formulation effluent. Journal of Environmental Management
Andreozzi R, Canterino M, Marotta R, Paxeus N (2005) Antibiotic removal from
wastewaters: The ozonation of amoxicillin. Journal of Hazardous Materials 122(3):243-
Ankley G, Brooks B, Huggett D, Sumpter J (2007) Repeating history: pharmaceuticals in the
environment . Environmental Science and Technology 41(24):8211–8217.
Arslan-alaton I, Dogruel S (2004) Pre-treatment of penicillin formulation effluent by
advanced oxidation processes Journal of hazardous materials 112:105−113.
Ashfaq A, Khatoon A (2014) Evaluating toxicological effects, pollution control and
wastewater management in pharmaceutical industry .International journal of current
research and academic review 2:2347-3215.
Aswini N, Sridevi V, Prasad MPD, Krishna AV (2014) Treatment of Pharmaceutical
Industrial Effluent By Microbial Fuel Cell (MFC). International Journal for Innovative
Research in Science & Technology 2:2349-6010.
Balcioglu IA, Otker M (2003) Treatment of pharmaceutical wastewater containing antibiotics
by O3 and O3/H2O2 processes. Chemosphere 50:85−95.
Chelliapan S, Wilby T, Sallis P (2006) Performance of an up-flow anaerobic stage reactor
(UASR) in the treatment of pharmaceutical wastewater containing macrolide antibiotics.
Water Research 40 (3):507-516.
Ctia O, Arminda A, Madeira LM (2014) Treatment of water networks (waters and deposits)
contaminated with chlorfenvinphos by oxidation with Fenton’s reagent. Chemical
Engineering Journal 241:190–199.
Daughton C, Ternes T (1999) Pharmaceuticals and personal care products in the environment:
agents of subtle change. Environmental Health Perspectives 107(S6):907–938.
Doll T, Frimmel F (2005) Cross-flow micro filtration with periodical back-washing for
photocatalytic degradation of pharmaceutical and diagnostic residues–evaluation of the
long-term stability of the photocatalytic activity of TiO2. Water Research 39(5):847-854.

Elmolla E, Chaudhuri M (2011) Combined photo-Fenton–SBR process for antibiotic
wastewater treatment. Journal of Hazardous Materials 192:1418–1426.
Elmolla E, Chaudhuri, M (2012) The feasibility of using combined Fenton-SBR for antibiotic
wastewater treatment. Desalination 285:14–21.
Enick O, Moore M (2007) Assessing the assessments: Pharmaceuticals in the environment.
Environmental assessment 27 (8):707-729.
Giri RR, Ozaki H, Ota S, Takanami R, Taniguchi S (2010) Degradation of common
pharmaceuticals and personal care products in mixed solutions by advanced oxidation
techniques. International Journal of Environmental Science and Technology 7 (2):251-
Giri RR, Ozaki H, Taniguchi S, Takanami R (2008) Photocatalytic Ozonation of 2, 4-
dichlorophenoxyacetic acid in water with a new TiO2 fiber. International Journal of
Environmental Science and Technology 5(1):17-26.
Gome A, Upadhyay K (2013) Biodegradability Assessment of Pharmaceutical Wastewater
Treated by Ozone. International Research Journal of Environment Sciences 2(4):21-25.
Hannah B, Sallis PJ, Yuzir A, Abdullah N, Chelliapan,S (2012) Chemical Oxidation Process
for the Treatment of Antibiotic Wastewater. International Journal of Engineering
Research and Applications 2:110-124.
Heberer T (2002) Occurrence, fate, and removal of pharmaceutical residues in the aquatic
environment: a review of recent research data. Toxicology Letters 131 (1-2):5-17.
Hussain S, Shaikh S, Farooqui M (2011) Chemical oxygen demand (COD) reduction of
Aqueous Active Pharmaceutical Ingredient of Isorobide 5-mononitrate waste water
streams by Advanced Oxidation-Fenton process based on H2O2/Fe+2 salt. Archives of
Applied Science Research 3(2):169-173.
Jones O, Voulvoulis N, Lester J (2007) The occurrence and removal of selected
pharmaceutical compounds in a sewage treatment works utilising activated sludge
treatment. Environmental Pollution 145 (3):738-744.
Kang Y W, Hwang KY (2000) Effects of reaction conditions on the oxidation efficiency in
the Fenton process. Water Research 34:2786-2790.
Karthikeyan S, Titus A, Gnanamani A, Mandal AB, Sekaran G (2011) Treatment of textile
wastewater by homogeneous and heterogeneous Fenton oxidation processes.
Desalination 281:438–445.

Khetan S, Collins T (2007) Human Pharmaceuticals in the Aquatic Environment: A
Challenge to Green Chemistry. Chemical Reviews 107(6):2319-2364.
Kolpin D, Furlong E, Meyer M, Thurman E, Zaugg S, Barber L, Buxton H (2002)
Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams,
1999–2000: a national reconnaissance. Environmental Science and Technology
Kulik N, Trapido M, Goi A, Veressinita Y, Munter R (2008) Combined chemical treatment of
pharmaceutical effluents from medical ointment production. Chemosphere 70:1525-
Kulik N, Trapido M, Goi A, Veressinina Y, Munter R (2008) Combined chemical treatment
of pharmaceutical effluents from medical ointment production. Chemosphere 70
Kumar S, Kanmani S (2010) Treatment of phenolic wastewaters in single baffle reactor by
solar/TiO2/H2O2 process. Desalination and Water Treatment 24:67−73.
Lalwani PK, Malu DD (2013) Reduction of Cod and Bod by Oxidation: A Cetp Case Study.
International Journal of Engineering Research and Applications 3:108-112.
Larsson D, Adolfsson-Erici M, Parkkonen J, Pettersson M, Berg A, Olsson P, Förlin L (1999)
Ethinyloestradiol — an undesired fish contraceptive. Aquatic Toxicology 45 (2-3):91-97.
Larsson DGJ, Fick J (2009) Transparency throughout the production chain-a way to reduce
pollution from the manufacturing of pharmaceuticals. Regulatory Toxicology and
Pharmacology 53(3):161-163.
Libing C, Jianlong W, Jing D, Haiyang L, Xulin S (2012) Treatment of coking wastewater by
an advanced Fenton oxidation process using iron powder and hydrogen peroxide. An
international Chemosphere journal 86:409–414.
Lillenberg M, Yurchenko S, Kipper K, Herodes K, Pihl V, Lõhmus R, Ivask M, Kuu A, Kutti
S, Litvin SV, Nei L (2010) Presence of fluoroquinolones and sulfonamides in urban
sewage sludge and their degradation as a result of composting. International Journal of
Environmental Science and Technology 7(2):307-312.
Madukasi EI, Dai X, He C, Zhou J (2010) Potentials of phototrophic bacteria in treating
pharmaceutical wastewater. International Journal of Environmental Science and
Technology 7 (1):165-174.

Miege C, Choubert J, Ribeiro L, Eusebe M, Coquery M (2009) Fate of pharmaceuticals and
personal care products in wastewater treatment plants – Conception of a database and
first results. Environmental Pollution 157 (5):1721–1726.
Miège C, Choubert J, Ribeiro L, Eusèbe M, Coquery M (2008) Removal efficiency of
pharmaceuticals and personal care products with varying wastewater treatment processes
and operating conditions – conception of a database and first results. Water Science and
Technology 57(1):49–56.
Nese E, Filiz NA (2013) Removal of COD and color from Direct Blue 71 azo dye wastewater
by Fenton’s oxidation: Kinetic study. Arabian Journal of Chemistry 10:S1158–S1163.
Oaks J, Gilbert M, Virani M, Watson R, Meteyer C, Rideout B, Shivaprasad H, Ahmed S,
Chaudhry MI, Arshad M, Mahmood S, Ali A, Khan A (2004) Diclofenac residues as the
cause of vulture population decline in Pakistan. Nature 427 (6975):630-633.
Renge VC, Khedkar SV, Bhoyar KS (2012) Micro pollutant Removal from Waste Water
Treatment Plant- A Review. International Journal of Advanced Engineering Technology
Rodrigues C, Madeira L, Boaventura R (2009) Optimization of the azo dye Procion Red H-
EXL degradation by Fenton’s reagent using experimental design. Journal of hazardous
materials 164:987–994.
Sebastián NS, Fernández JF, Segura XF, Ferrer AS (2003) Pre-oxidation of an extremely
polluted industrial wastewater by the Fenton’s reagent. Journal of Hazardous Materials B
Sirtori C, Petrovic M, Radjenovic J (2009) Solar photocatalytic degradation of persistent
pharmaceuticals at pilot-scale: Kinetics and characterization of major intermediate
products. Applied Catalysis 89:255−264.
Soraya M, Hamidi AA, Mohamed HI, Mohammed JKB, Mohajeri L (2010) Influence of
Fenton reagent oxidation on mineralization and decolorization of municipal landfill
leachate. Journal of Environmental Science and Health Part A 45:692–698.
Sreekanth D, Sivaramakrishna D, Himabindu V, Anjaneyulu Y (2009) Thermophilic
treatment of bulk drug pharmaceutical industrial wastewaters by using hybrid up flow
anaerobic sludge blanket reactor. Bioresource Technology 100(9):2534-2539.
Stumm-Zollinger E, Fair GM (1965) Biodegradation of steroid hormones. Research Journal
of the Water Pollution Control Federation 37(11):1506–1510.

Suarez S, Lema J, Omil F (2009) Pre-treatment of hospital wastewater by coagulation–
flocculation and flotation. Bioresource Technology 100 (7):2138-2146.
Tekin H, Bilkay O, Ataberk SS, Balta TH, Ceribasi IH (2006) Use of fenton oxidation to
improve the biodegradability of a pharmaceutical wastewater. Journal of hazardous
materials 136:258–265.
Tiwari AK and Upadhyay VK (2013) Fenton’s reagent dose calculation with respect to COD
value and the process requirement optimization for effective oxidation of Aqueous
Mother Liquor Effluent of an API manufacturing industry. International Journal of
Advanced Research 1:158-164.
VANERKAR AP, SHANTA S, DHARMADHIKARI DM (2013) Full Scale Treatment of
Herbal Pharmaceutical Industry Wastewater. International Journal of Chemical and
Physical Sciences 2: 2319-6602.
Watkinson A, Murby E, Costanzo S (2007) Removal of antibiotics in conventional and
advanced wastewater treatment: Implications for environmental discharge and
wastewater recycling. Water Research 41 (18):4164-4176.
Webb S, Ternes T, Gibert M, Olejniczak K (2003) Indirect human exposure to
pharmaceuticals via drinking water. Toxicology Letters 142 (3):157-167.
Yazdanbakhsh AR, Sheikh MA, Mahdieh S, Hatam G, Mohammad A (2014) Cod Removal
From Synthetic Wastewater Containing Azithromycin Using Combined Coagulation
And A Fenton-Like Process. Environmental Engineering and Management Journal