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Journal of the Taiwan Institute of Chemical Engineers


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Processing of pharmaceutical effluent condensate by nanofiltration


and reverse osmosis membrane techniques
Yerrapragada Venkata Lakshmi Ravikumar 1, Swayampakula Kalyani 1,
Suggala Venkata Satyanarayana 2, Sundergopal Sridhar 1,*
1
Membrane Separations Group, Chemical Engineering Division, Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad 500 007, India
2
Chemical Engineering Department, JNTUA, Ananthapur 515002, India

A R T I C L E I N F O A B S T R A C T

Article history: Nanofiltration (NF) and reverse osmosis (RO) are well-established processes for desalination of sea and
Received 11 December 2012 ground water besides treatment of industrial effluents. Pharmaceutical effluents usually contain organic
Received in revised form 24 September 2013 and inorganic waste materials that contribute to total dissolved solids (TDS), chemical oxygen demand
Accepted 29 September 2013
(COD) and biochemical oxygen demand (BOD), rendering the mode of treatment highly challenging. In
Available online xxx
the present investigation, performance of hydrophilized polyamide (HPA-250) NF and thin film
composite (TFC) polyamide RO membranes has been studied for the treatment of pharmaceutical
Keywords:
effluent condensate. Effect of applied pressure on separation performance on NF/RO membranes was
Nanofiltration
Reverse osmosis
investigated for both non-aerated (Feed A) and aerated (Feed B) condensates. Influence of concentration
Pharmaceutical effluent polarization and fouling on membrane performance parameters such as flux, water recovery and
Aerated and non-aerated condensate rejection was evaluated as a function of time. A comparative study on treatment of aerated and non-
Economic estimation aerated feed samples was carried out with respect to flux and rejection of TDS, COD and BOD. At a
constant feed pressure of 10.34 bar, %rejection of TDS was found to be 78.14 for Feed B and 75.24 for Feed
A in NF process whereas the corresponding values for RO were 95.30% and 91.76%. COD removal
efficiencies in the same order were observed to be 94.30% and 93.09% for NF and 99.50% and 98.33% for
RO. Design and economic estimation of commercial NF/RO systems for processing of 1000 L/h
pharmaceutical condensate was carried out. NF process was found to more economical than RO due to
advantage of greater flux leading to requirement of lower operating pressures.
ß 2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction evaporator established as the final step in the effluent treatment


plant (ETP) of a pharmaceutical industry [5]. From the evaporator
Pharmaceutical industries are one of the major water polluting vapor passes into the cooling chamber in which they are cooled to
industries in the world, discharging huge quantities of wastewater form condensate which is then treated by activated sludge process
containing organic solvents, catalysts, reactants, intermediates, (ASP) also called aerobic process [6]. However, biological methods
raw materials and drug intermediates [1,2]. The presence of these including aerobic and anaerobic processes cannot always reduce
toxic recalcitrant substances in industrial effluents lowers the the TDS and color contents to meet the required wastewater
efficiency of methods employed for removal of chemical oxygen disposal standards [7]. Therefore, a study using eco-friendly
demand (COD). Due to the emergence of environmental con- alternative separation methods to treat this type of effluent
sciousness, the pollution control boards have enforced stricter and condensate was considered to be worthwhile [8].
stringent norms pertaining to effluent disposal [3]. Scarcity of Membrane processes have the ability to exhibit greater
water is an added incentive for treatment of industrial effluents to efficiency for separation of COD, BOD and TDS from the condensate
recover recyclable water. However, for the treatment of an effluent such that it can recycled in the industry or discharged with
by conventional methods like aerobic and non-aerobic digestion, pollutant levels within the range specified by Pollution Control
the ratio of BOD to COD should be >0.6 [4]. Boards. Membrane techniques such as nanofiltration (NF) and
Condensate is a liquid, which is formed by cooling or reverse osmosis (RO) have been gaining considerable attention in
compressing vapors coming from an evaporation process. In the the recent past for water and wastewater treatment. These
present context, the condensate comes from a multiple effect techniques can effectively separate organic and inorganic com-
pounds from industrial effluents besides TDS and microorganisms
from drinking water [9–13]. In fact, application of NF/RO could be
* Corresponding author. Tel.: +91 4027191394; fax: +91 4027193626.
extended to deal with two major separation problems faced by the
E-mail address: sridhar11in@yahoo.com (S. Sridhar). pharmaceutical industry which includes treatment of wastewater

1876-1070/$ – see front matter ß 2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jtice.2013.09.021

Please cite this article in press as: Ravikumar YVL, et al. Processing of pharmaceutical effluent condensate by nanofiltration and reverse
osmosis membrane techniques. J Taiwan Inst Chem Eng (2013), http://dx.doi.org/10.1016/j.jtice.2013.09.021
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and concentration of valuable organic compounds. Several Table 1


Feed characteristics of pharmaceutical effluent condensate.
researchers have been investigating the mechanism of rejection
executed by NF/RO membranes [14,15]. However, these investiga- Parameters Feed characteristic
tions were performed merely on a laboratory scale and in most pH 9.8
cases with demineralized water. There are few reports published TSS, ppm 829
on the performance of full-scale NF/RO process for separation of TDS, ppm 33
micro-pollutants such as endocrine disrupting compounds (EDCs) Chlorides, mg/L 157
Sulphates, mg/L 160
and pharmaceuticals [16,17], with no study reporting complete
COD, mg/L 9670
removal. Since the pores in NF membrane are more open than in BOD, mg/L 3300
RO, the former exhibits greater flux. The development of NF Oil grease, mg/L 7.55
technology as a viable process in the last decade has led to a Viscosity, mPa s 1500
marked increase in its adoption for processing effluents from
different industries [18–20].
The objective of present study is to study effectiveness of NF
and RO pilot-scale systems to process non-aerated and aerated were procured from M\s Hach, Bangalore, India. Conductivity meter
effluent condensate samples coming from pharmaceutical indus- (DCM-900) and pH meter (DPH-504) were purchased from Global
try. The effect of operating variables such as feed pressure, feed Electronics, Hyderabad, India.
concentration and fouling on membrane performance with respect
to water flux and %rejection of TDS, COD and BOD has been 2.2. Membrane structural description
extensively studied. Design and economic estimation of commer-
cial NF/RO systems for processing of 1000 L/h pharmaceutical NF and RO membranes for treating the effluent were made of
condensate has been carried out. aromatic polyamide (PA) deposited on polyethersulfone (PES)
substrate by interfacial polymerization using different reagents,
while PES was produced by phase inversion technique [21,22]. The
2. Experimental
highly advanced NF membrane used in this work is a hydrophilized
version of PA synthesized by coating a lean solution of
2.1. Materials
polyvinylalcohol (PVA) on PA followed by thermal crosslinking.
Fig. 2 represents the physical structure of HPA-250 polyamide
Commercial membrane modules of specification 2040 and
composite NF membrane comprising of four layers made of
material hydrophilized polyamide HPA-250 for NF and TFC
different materials.
polyamide for RO in spiral wound configuration having effective
area of 2.5 m2 each were procured from Permionics Membranes Pvt.
2.3. Description of NF/RO system
Ltd., Vadodara, India. The specification indicates that the diameter of
the spiral module was 2.0 in. and length 40 in. The pharmaceutical
Fig. 3 provides a schematic representation of pilot scale NF/RO
condensate effluent was collected from Hygro Chemicals Pharmtek
system. A feed tank of 100 L capacity was provided for storage and
Pvt. Ltd., Bolarum, Narsapur, Medak Dist., A. P., India. Fig. 1 shows
supply of effluent condensate to the system. An inexpensive
the industrial process flow diagram wherein effluent condensate
micron rope cartridge made of hydrophobic polypropylene (PP),
gets generated and respective feed characteristics are depicted in
having contact angle of 1028 and 5 mm pore size, was installed
Table 1. Non-aerated condensate is depicted as Feed A and the
upstream of the spiral wound membrane module as a prefilter. The
aerated one as Feed B. Potassium dichromate, ferrous ammonium
cartridge is used to prevent the entry of suspended solid particles
sulfate, mercuric sulfate, sulfuric acid, ferroin indicator for COD
which could damage the membrane while its porous nature
analysis, sodium thiosulfate, Wrinkler’s reagent, MnSO4, potassium
ensures a very small pressure drop. The cartridge can be replaced
iodide, starch indicator for BOD analysis, citric acid, HCl, EDTA,
once it gets fouled and can be recycled a couple of times by treating
NaOH, and sodium metabisulphite (SMBS) for washing and storing
with dilute acid. A high pressure pump (Hironisha, Japan) capable
of the membranes were purchased from sd Fine Chemicals Ltd.,
of maintaining a pressure up to 50 bar was installed for
Mumbai, India. Deionized water for cleaning and varying of feed
transporting the feed liquid throughout the system. The pump
concentration was generated from the same pilot RO system used in
was run by a 2 HP single phase motor (Crompton, India). A
the studies. BOD incubator (RCI-S.NO-313, India), COD analyzer
restricting needle valve was provided on the reject outlet of the
(DRB 200 COD Reactor, Germany) and Colorimeter (Hach-DR-890)
membrane pressure vessel, to pressurize the feed to the desired
value indicated by a pressure gauge installed upstream of the
valve. The feed tank had a provision for recycle of the reject which
passed through a heat exchanger for maintaining constant
temperature (28–30 8C), especially since polyamide is susceptible

Fig. 2. Physical structure of four layered HPA-250 composite nanofiltration


Fig. 1. Flow sheet of effluent processing at pharmaceutical industry. membrane.

Please cite this article in press as: Ravikumar YVL, et al. Processing of pharmaceutical effluent condensate by nanofiltration and reverse
osmosis membrane techniques. J Taiwan Inst Chem Eng (2013), http://dx.doi.org/10.1016/j.jtice.2013.09.021
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Fig. 3. Process flow diagram of NF/RO membrane pilot plant of given 1000 L/h capacity.

at operating temperatures above 45 8C. At the end of the 2.4. Description of multiple effect evaporator (MEV)
experiment the reject was fed to a multiple effect evaporator
(MEV) for further removal of water and generate solids which are To increase the steam economy of the evaporator, a series of
easily disposed off in landfills. Permeate and reject flow rates were evaporators are employed between steam supply and condensate.
measured using rotameters containing metal floats. Fig. 4 shows the schematic representation of multiple effect

Fig. 4. Schematic representation of three stage multiple effect evaporator (MEV).

Please cite this article in press as: Ravikumar YVL, et al. Processing of pharmaceutical effluent condensate by nanofiltration and reverse
osmosis membrane techniques. J Taiwan Inst Chem Eng (2013), http://dx.doi.org/10.1016/j.jtice.2013.09.021
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evaporator. Fresh feed, which is the final reject coming from NF/RO where Cp is concentration of solute in permeate and Cf its
process, is fed to the first stage of the evaporator where steam is concentration in feed.
used as heating medium introduced through steam chest of the The flux (J) is the volume of permeate (V) collected per unit
first stage. The vapors produced from the first stage are passed to membrane area (A) per unit time (t):
the steam chest of the second stage and concentrated liquor from
first stage is fed to the second stage. Similarly, in series mode, the V
J¼ (2)
vapors produced from the second stage are fed to the steam chest At
of the third stage and concentrated liquor from second stage is fed
to the next stage and so on. The vapor produced in the last (third)
2.7. Membrane fouling and its prevention
stage is passed through the condenser. Cooling water flows
through the tubes of the condenser and the vapor is condensed and
Fouling of the membranes takes place due to the formation of
collected as liquid for reuse.
calcium carbonate and sulfate scales on the surface over a period of
time. In case of NF, plugging of pores by solute particles can also
2.5. Experimental procedure
occur in addition to scale deposition. The effluent used in the
present study contains chlorides, sulphates and hardness which
The feed tank was filled with 50 L of feed solution. The solution
can foul the membrane. Occurrence of chemical scales was
was pumped using a single stage low pressure centrifugal pump
prevented to a significant extent by dosing an aqueous antiscalant
through the pre-filter assembly consisting of sand filter, activated
comprising of 10 ppm sodium hexametaphosphate into the feed
carbon column and micron filter to remove colloidal impurities
pipeline. However, to restore flux which underwent a reduction
and suspended solids before they reach the membrane module.
over a period of time, the membrane was cleaned with 1% (w/v)
The system was initially run to remove 2.2 L of distilled water
citric acid for 15 min at the end of the day to remove mineral scales
present as dead volume in the system. The high pressure pump was
followed by circulation of 1% NaOH + 0.5% EDTA (w/v) aqueous
then employed to transport the feed through spiral wound
solution for 10 min to remove stubborn organic foulants, once
membrane module and the system pressure was maintained at
every 15 days.
a constant value by means of a needle valve. The retentate flow rate
To prevent biological fouling, which is an irreversible phenom-
was maintained at constant value of 10 L/min throughout the
enon, the membrane was stored in 0.5% (w/v) sodium metabisul-
experiment to ensure similar hydrodynamic conditions inside the
phite (Na2S2O5).
membrane module. The study was a single stage batch process
with complete retentate recycles. The feed pressure was varied
3. Results and discussions
from 3 to 28 bar for Feeds A and B. Permeate flow was recorded and
samples of reject and permeate were collected for the analysis of
3.1. Effect of pressure on flux and TDS %rejection
BOD, COD and TDS at regular time intervals.

The effect of feed pressure on flux of permeate for Feeds A and B


2.6. Analytical methods
for both NF and RO processes are shown in Fig. 5. The permeate
flux increases linearly with pressure. Flux is greater for NF when
2.6.1. Measurement of total dissolved solids (TDS)
compared with RO in case of both non-aerated and aerated feed
Conductivity of feed and permeate samples were measured using
conditions. Further, flux for Feed B is generally higher than that
digital conductivity meter (DCM-900) whereas TDS was measured
recorded with Feed A (non-aerated). At a constant pressure of
by slow heating of a known volume of sample (10 mL) taken on a
10.34 bar, the flux values of NF and RO membranes were found to
pre-weighed empty glass Petri dish at 105 8C using a sand bath
be 32 and 15.23 L/m2 h for Feed A whereas it was 34.4 and 16.4 L/
heater. The weight of residual solids was recorded in an accurate
m2 h, respectively when feed was aerated (Feed B). The flux for
weighing balance after entire liquid on Petri dish got evaporated and
Feed B increased linearly from 34 to 160 L/m2 h for NF and 16 to
TDS for known volume was determined as the difference in weight
60 L/m2 h in case of RO. The pore size in NF membranes is usually
for further calculated in proportion to 1 L of sample volume.
ten times greater than that in RO film and moreover the NF
membrane in this case is hydrophilized for enhanced affinity with
2.6.2. Measurement of chemical oxygen demand (COD)
water which explains greater flux observed in case of the former.
COD is the measure of oxygen consumed during the oxidation of
Integration of aerobic process and membrane separation can
the organic matter present in water by a strong oxidizing agent.
COD value of feed and permeate samples were measured by open
reflux method, following standard methodologies [23].

2.6.3. Measurement of biochemical oxygen demand (BOD)


BOD is the measure of degradable organic material present in
the sample and can be defined as the amount of oxygen required by
the microorganisms in stabilizing the biologically degradable
organic matter under aerobic condition. The principle of the
method involves measuring of the difference in oxygen required by
the sample’s organic matter for degradation before and after
incubation for 5 days [24].

2.6.4. Calculation of percent rejection (%R) and flux (J)


Separation performance of the membrane is denoted in terms of
%rejection of TDS and flux, calculated by

1  Cp
%R ¼  100 (1)
Cf Fig. 5. Effect of feed pressure on flux of NF and RO for Feed A and Feed B samples.

Please cite this article in press as: Ravikumar YVL, et al. Processing of pharmaceutical effluent condensate by nanofiltration and reverse
osmosis membrane techniques. J Taiwan Inst Chem Eng (2013), http://dx.doi.org/10.1016/j.jtice.2013.09.021
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Fig. 6. Effect of feed pressure on TDS %rejection of NF and RO for Feed A and Feed B
samples. Fig. 8. Effect of feed pressure on permeate COD levels for NF and RO trials carried out
with Feeds A and B.
produce improved solute rejection due to lowering of COD load on
the latter as seen in case of Feed B. constant feed pressure of 10.34 bar with permeate being evaluated
Fig. 6 shows the effect of feed pressure (3–28 bar) on for conductivity and flow rate at regular time intervals of 5 min each
performance of NF/RO membranes in terms of % TDS rejection until the flux attained a constant value known as steady state flux
for Feeds A and B. When the trans-membrane pressure increased (SSF). Permeate was collected over a duration of 30–50 min until
from 3 to 28 bar, the TDS %rejection increased rapidly up to the desired water recovery was achieved. The %recovery increased
13.8 bar, beyond which significant changes were not observed for with time, whereas the flux decreased due to a rise in feed
both types of feeds. At a trans-membrane pressure of 13.8 bar the concentration. The average values of water recovery increased from
rejection was found to be 76.7% for Feed B and 75.0% for Feed A in 8% to 60% during NF operation and 10% to 70% in case of RO while
NF process while corresponding observations for RO were 93.6% the corresponding NF flux decreased from 60 to 30 L/m2 h and for
and 91.8%. Increase in rejection of TDS with rise in applied pressure RO from 30 to 15 L/m2 h as depicted in Fig. 7 for Feeds A and B.
could be explained on the basis of solution-diffusion mechanism Increasing concentration of solute (TDS) molecules in the feed with
[25] which states that water sorption by the hydrophilic operating time increases concentration polarization of these
membranes gets enhanced due to the presence of –CONH polar molecules on the NF/RO membrane surface as well as osmotic
functional groups which indulge in hydrogen bonding with H2O pressure resulting in a corresponding decrease in trans-membrane
molecules. In case the NF membrane –OH groups are also present pressure difference across the barrier and reduction in flux [28,29].
in addition to amide moieties. On the other hand, solute molecules
(TDS) do not interact with the membrane and their flux remains 3.3. Variation of permeate COD with feed pressure
more or less the same [26,27].
From Fig. 8 it can be observed that the COD content in permeate
3.2. Variation of flux and %recovery with time decreased from 200 to 10 ppm and 170 to 10 ppm for RO and NF trials
conducted with Feed A. On the other hand the corresponding values
Fig. 7 represents the variation in flux and %recovery with decreased from 190 to 10 ppm for RO and 160 to 10 ppm in case of NF
operating time for Feeds A and B with respect to NF and RO for Feed B as observed from the same figure. As concentration
processes, respectively. The experiments were conducted at a polarization increased, separation performance declined due to

Fig. 7. Variation of flux and %recovery with time for NF and RO processes conducted Fig. 9. Variation in NF and RO fluxes with time of operation of experiments
with Feeds A and B. conducted with Feeds A and B.

Please cite this article in press as: Ravikumar YVL, et al. Processing of pharmaceutical effluent condensate by nanofiltration and reverse
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Table 2
Equipment list and capital cost for NF and RO systems.

Item Capacity/size MOC Quantity Cost (USD)

Unit Total

Membrane housing – 1 190 190


TFC poly amide membrane modules for RO (2.500 dia  4000 long) PA 1 300 300
HP 250 membrane for NF (2.000 dia  4000 long) PA 1 300 300
1354 pressure vessel 35 lpm – 1 200 200
Skid SS 1 200 200
Filter assembly 35 lpm PP 2 7.5 15
Feed pump (2.5 HP) 35 lpm – 1 116 116
1 HP high pressure pump 35 lpm SS 1 1200 1200
40 Nb TMF (multiport valve) – – 2 60 120
Online TDS meter – – 1 79 79
Sand & pebbles – – 3 Bags 10 30
Cleaning pump 2 lpm SS316 1 116 116
3 Phase control panel – SS 350/500 1 170 170
Carbon bags – – 2 60 120
Hard ware lot – UPVC 1 set 200 200
Ozonator – – 1 300 300
UV system – – 1 300 300
Total cost 3656

PP, polypropylene; PA, polyamide; SS, stainless steel; UPVC, unplasticized polyvinyl chloride; lpm, liters per minute.

lowering in trans-membrane pressure gradient, which is the NF and RO membrane flux for both non-aerated and aerated
difference between applied pressure and osmotic pressure. condensate feeds. Membrane cleaning and storage were con-
ducted at 3 bar for 10–15 min with reagents indicated in Section
3.4. Membrane cleaning 2.7. After chemical washing flux values improved from 22.04 to
44.24 L/m2 h for NF and 7 to 20 L/m2 h for RO, which nearly attain
Membrane maintenance was carried out at regular frequency of original fluxes of 46 and 21 L/m2 h for Feed A after first 15 days of
every 15 days by chemical cleaning to control fouling and recover operation. A similar trend was observed in case of aerated feed
flux. Fig. 9 depicts the effect of chemical cleaning on restoration of (Feed B) through an increase in NF flux from 23.1 to 45.8 L/m2 h

Table 3
Operation and maintenance cost for NF and RO systems.

NF RO

Module replacement cost 670


Duration of replacement (years), NF/RO 5/3
No. of working hours/day (NF/RO) 12/22
Cost/h (USD) 0.0372 0.062
Cartridge replacement cost
No of cartridges (NF/RO) 2/3
Total cartridge replacement cost (@ 8 USD) 16 24
Duration of replacement (days) 90
Cost/h (USD) 0.0148 0.012
Power cost
Feed pump (KW) (NF/RO) 1.12/0.3725
Dosing systems (KW) (NF/RO) 0.015/0
High pressure pump (KW) (NF/RO) 1.85/0.3725
UV lamp (KW) (NF/RO) 0.072/0.072
Ozonator (KW) (NF/RO) 0.1/0.1
Total power consumption (KW) (NF/RO) 3.157/0.917
Hourly cost (@ 0.1 USD) 0.0825 0.284
Chemical consumption
Antiscalant dosing (ppm) 5
Dosage (L/h) 0.01
Cost/L (USD) 6.4
Hourly cost (USD) 0 0.064
CIP Chemicals (EDTA, NaOH, citric acid)
Frequency for NF and RO (days) 15
Total cost of CIP per hour (USD) 0.0452 0.0452
Total operating cost per hour (USD) 0.1653 0.433
Total operating cost per year assuming 22 h and 12 h of operation/day for RO & NF. (USD) 724 3477
Depreciation cost (assuming 10% of capital cost) (USD) 92 402.6
Labor cost per year + raw water (USD) 2500 2660
Total cost per year (USD) 3316 6539
Permeate
Quantity (L/h) 1000/1800 1800 1000
Operation time (h) 22/12 12 22
Quantity of permeate generated in 1 year (kL/year) 8030/7884
Cost/kL of permeate (USD) 0.4206 0.814
If sold at 4  103 USD/L
Annual profit (USD) 28220 25583.58
Pay back period (year) 0.12 0.25

Please cite this article in press as: Ravikumar YVL, et al. Processing of pharmaceutical effluent condensate by nanofiltration and reverse
osmosis membrane techniques. J Taiwan Inst Chem Eng (2013), http://dx.doi.org/10.1016/j.jtice.2013.09.021
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and RO flux from 8.8 to 21.5 L/m2 h after the same operating conducting this project study under XII Five Year Plan MATES
period (Fig. 9). Therefore, restoration of flux for every 15 days of Network Project.
operation was found to be 96.24% and 95.36% with Feed A for NF
and RO membranes respectively, whereas the corresponding
values for Feed B (aerated) were 98.29% and 97.28%. References

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Please cite this article in press as: Ravikumar YVL, et al. Processing of pharmaceutical effluent condensate by nanofiltration and reverse
osmosis membrane techniques. J Taiwan Inst Chem Eng (2013), http://dx.doi.org/10.1016/j.jtice.2013.09.021

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