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Tratamiento de Efluentes Farmaceuticos - Nanofiltracion y Osmosis Inversa
Tratamiento de Efluentes Farmaceuticos - Nanofiltracion y Osmosis Inversa
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.
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
G Model
JTICE-755; No. of Pages 7
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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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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
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
G Model
JTICE-755; No. of Pages 7
4 Y.V.L. Ravikumar et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (2013) xxx–xxx
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.
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
osmosis membrane techniques. J Taiwan Inst Chem Eng (2013), http://dx.doi.org/10.1016/j.jtice.2013.09.021
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Table 2
Equipment list and capital cost for NF and RO systems.
Unit Total
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
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