Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Published on 15 July 2014. Downloaded by Central Salt & Marine Chemicals Research Institute (CSMCRI) on 22/01/2015 08:12:53.
The development of a low-cost, high-performance, biobased membrane technology has been attempted
to treat environmentally sensitive wastewater streams. Novel foam membranes (FMs) were derived from
agarose (Agr) and gelatin (Gel) in combination with a non-toxic fruit extract and natural crosslinker,
genipin (G). FMs were successfully tested for their oil–water separation efficiencies. FMs attained unique
capillary microstructures (10–45 µm) as a result of the controlled lyophilization process, which allows
Received 10th June 2014, selective permeation of water. Stable microporous membranes with nominal pore sizes in between the
Accepted 14th July 2014
microfiltration and ultrafiltration range generated as high as >500 L m−2 h−1 continuous flux with ∼98% pure
DOI: 10.1039/c4gc01070a product water. One of the advantages of these FMs is that after oil–water separation, they can undergo an
www.rsc.org/greenchem easy membrane cleaning process, thereby retaining surface activity for long term performance.
4552 | Green Chem., 2014, 16, 4552–4558 This journal is © The Royal Society of Chemistry 2014
View Article Online
This journal is © The Royal Society of Chemistry 2014 Green Chem., 2014, 16, 4552–4558 | 4553
View Article Online
mixture. A booster pump was used to circulate the oil–water The % rejected oil in the permeate was calculated using
mixture into a feed chamber. Each permeate sample was equation:
Published on 15 July 2014. Downloaded by Central Salt & Marine Chemicals Research Institute (CSMCRI) on 22/01/2015 08:12:53.
Fig. 2 Scheme representing FM formation mechanism under the influence of genipin cross-linking and the hydrogen bonding interaction between
agarose-gelatin co-gels. Crosslinking agent, time and freeze-drying process drive the pore formation and their morphology in foam membranes.
4554 | Green Chem., 2014, 16, 4552–4558 This journal is © The Royal Society of Chemistry 2014
View Article Online
result, co-gel colour transforms into blue soft matter.19 Once cation. However, characteristic bands of gelatin at 1640, 1530
the genipin crosslinking was completed, the gel was lyophi- and 1240 cm−1 (due to the amide linkage) also appear in the
Published on 15 July 2014. Downloaded by Central Salt & Marine Chemicals Research Institute (CSMCRI) on 22/01/2015 08:12:53.
lized. Under lyophilization, ice crystals readily formed in the final products. The main noticeable change appeared in the
agarose column assembly, which was then subjected to the shift of the broader Agr stretching peak (OH) at ∼3438 cm−1
sublimation process, leaving behind porous voids and agarose upon blending with Gel (∼3435 cm−1) to 3398 cm−1. This
layers on the gelatin wall, which was regulated from hydrogen remained unchanged upon genipin crosslinking. Therefore,
bonding.20 hydroxyl (OH) groups present in agarose engage in hydrogen
To prove the proposed mechanism, membranes were exten- bonding interactions with the N lone pair of the amide
sively characterised for their characteristic changes using group of gelatin, resulting in a lamellar structure in which
FTIR, TGA, solid UV analysis as well as NMR analysis. In the gelatin holds agarose on either side. Therefore, it confirms that
FTIR analysis in Fig. 3(a), agarose exhibited characteristic the superhydrophilic agarose micro-pore is surrounded by gelatin
peaks at 932 cm−1 (due to the 3,6-anhydrogalactose linkage), walls used for selective separation from oil–water mixtures.
1162 cm−1 and 1076 cm−1.17 The gelatin spectrum showed Furthermore, thermogravimetric (TGA) and UV-visible spec-
characteristic absorption bands at 3436, 2925, 1640 and troscopic tools were used to determine the nature of mem-
1530 cm−1, which correspond to –OH, amine (N–H), amide I brane transformation and membrane stability. TGA results
(CvO) and amide II (NH2), respectively. Appearance of charac- (see Fig. 3(b)) of the blend prepared in the presence of cross-
teristic peaks in the FTIR spectrum of Ag + Gel + Gen confirms linking agent showed the high thermal stability in comparison
that the main characteristic absorption bands of agarose to pristine constituents. Minimum residual masses of 20.53%
(1162, 1076 and 932 cm−1) remained intact during modifi- and ∼25% were obtained for Agr and Agr + Gel blends, respect-
ively. However, the genipin cross-linked blend (Agr + Gel +
Gen) retained as high as 40.08% residual mass at 599.5 °C.
Therefore, this result directly indicates that there exists a rigid
network as a result of genipin crosslinking in FM.21 Control
and cross-linked blend FM samples were analysed using solid
UV spectroscopy. In Fig. 3(c), the pristine genipin in water
exhibited a characteristic peak at 240 nm, whereas the control
Agr + Gel blend had none. However, genipin crosslinked blend
(Agr − Gel + Gen) exhibited a shift in the characteristic genipin
peak to 280 nm with the appearance of an additional peak at
590 nm. This confirms the extended conjugation of genipin
crosslinking, which induces the dark blue color in FMs seen at
590 nm.22 In addition to this, the crosslinking of the amino
group was further confirmed by the disappearance of the
amine proton in the 1H NMR of the cross-linked FMs, which
occurs in the range of 7–8 ppm (see ESI Fig. S1†).
Furthermore, membrane swelling ought to be stabilized
before fixing them to the separation cell or crossflow set-up.
We performed a swelling study of FM with different cross-
linking ratios of genipin added. As adequate crosslinking
strongly adds stability to microstructures, 0.01%, 0.02%,
0.03%, 0.04% and 0.05% (w/v, with respect to total solution)
genipin cross-linked blend membranes (2% w/v) were
measured for their swelling properties in pure water and
water–oil (80 : 20) mixtures. Fig. S2† shows swelling behaviour
of control, 0.01%, 0.02%, 0.03%, 0.04% and 0.05% (w/v)
genipin in constant 2% w/v gelatin–agarose blend mixtures.
Results showed that stable microstructures were yielded with
0.04% (w/v) genipin cross-linked membrane with ∼70% swel-
ling in both pure water and 20 : 80 oil–water mixtures in com-
parison to 0.01%, 0.02% (>80%) and 0.03% (<60%) added
genipin, which resulted in a soft unstable membrane. More-
Fig. 3 FTIR analysis of bio-based FM from pristine to final composition over, 0.05% genipin cross-linked FM exhibited similar swelling
(a) Agr, Gel, Agr + Gel blend and genipin crosslinked Agr + Gel, (b) thermo-
as observed for 0.04% genipin cross-linked FM.
gravimetric analysis of pristine, blend and cross-linked FMs, (c) solid
UV-spectroscopic measurement recorded on genipin powder, blend and
Fig. 3(d) shows the appearance and texture of cross-linked
cross-linked FM, and (d) actual photographic images of foam membranes, FMs with different blend concentrations in comparison with
from control to cross-linked Agr + Gel with different blend concentrations. pristine blend foam. It is also evident from the images that the
This journal is © The Royal Society of Chemistry 2014 Green Chem., 2014, 16, 4552–4558 | 4555
View Article Online
microstructure in the 2% w/v blend membrane is more mixtures. Fig. 4(d) displays the permeate flux and % rejection
uniform and compact. With this, further experiments were of various mixtures, namely, oil spill, hexane–water, crude oil–
Published on 15 July 2014. Downloaded by Central Salt & Marine Chemicals Research Institute (CSMCRI) on 22/01/2015 08:12:53.
designed to evaluate water selectivity and separation efficiency water, toluene–water and edible oil–water mixtures.
using the optimized 0.04% (w/v) genipin (2% w/v blend) cross- The concentration of oil-in-water calculated from Fig. 4(b) and
linked membrane. (c) were then plotted against permeate flux to determine the mem-
Fig. 4(a) shows characteristic photographic images of lab- brane performance. From figure it is clear that 500 L m−2 h−1
scale experiments for oil–water separation conducted under fluxes yielded with added >97% purity to water. It is also
gravity. Several oil–water mixtures were subjected to a selective important that the flux and rejections were identical and
separation process under gravity as described in the Experi- independent of feed nature.
mental section. Considering water as the rich phase in the Separation of oil–water phases under gravity is a simple
permeate, infrared (IR) spectroscopy was used as a tool to process and follows the principle of dead end filtration. In the
quantify the amount of oil diffused in the permeate water. long term, it is expected that the membrane not only allow the
Prior to permeate sample analysis, we calibrated standard passage of water but also absorb oil, which reduces the separ-
curves for different concentrations of oil-in-water. Six standard ation selectivity and efficiency. In such situations, membrane
solutions over the range from 1 to 100 mg L−1 oil-in-water were performance can be accelerated by the assistance of cross flow
prepared for stable emulsion using a sonication bath. Further- pressure. Moreover, in oil-in-water type emulsions, oil is the
more, these samples were subjected to FTIR analysis. The internal dispersed or discontinuous phase, while water is the
established calibration range fit well with linearity and accu- external or continuous phase. Crossflow velocity and the con-
racy observed with a correlation coefficient of R2 = 0.99957 and tinuous flow help the membrane to enhance the separation
a standard error of prediction of 0.247 mg ml−1 obtained. process. To test the efficiency membranes for their long term
Fig. 4(b) shows the characterization of crude oil in the perme- performance and stability, a stable emulsion was pumped to
ate, where the disappearance of the characteristic peaks at the feed chamber, which led to continuous contact with the
1745 and 2930 cm−1 (for CvO of esters and C–H stretching of feed and the membrane. Fig. 5(a) and (b) show typical images
oils, respectively) indicates the oil content in the permeate was of experimental setups used for several oil–water separation
negligible. Fig. 4(c) shows the characterization of hexane in experiments (see Video File S1†). In an oil–water emulsion,
the permeate, where the disappearance of characteristic peaks water molecules adsorb on the oil droplet, forming a stable
at 1465 and 2960 cm−1 for CH2 bending and C–H stretching of suspension. When the emulsions were exposed to superhydro-
hexane, respectively, indicates that an insignificant quantity of philic FM, the water molecular film broke, resulting in aggre-
hexane diffused into the permeate. Similar results were also gation of water droplets. Moreover, crossflow velocity of feed
observed for oil spill, edible oil–water and toluene–water assists in driving the larger aggregated water droplets to pass
through the bio-based FM pores, leaving behind oil. Fig. 5(c)
and (d) gives a complete assessment of foam membranes
for their flux and rejection of crude oil and hexane from
water-rich streams.
4556 | Green Chem., 2014, 16, 4552–4558 This journal is © The Royal Society of Chemistry 2014
View Article Online
As mentioned earlier, membranes were tested under cross- 3.1 Biodegradability factor
flow pressure (∼0.2 bar) using crossflow velocity of feed. There For sustainable and clean process, preparing a biodegradable
Published on 15 July 2014. Downloaded by Central Salt & Marine Chemicals Research Institute (CSMCRI) on 22/01/2015 08:12:53.
has been a substantial increase in rejection observed for both membrane is not only the desired target, but also expected to
the mixtures. Even though initial cycles have shown results perform efficiently long term in its life time. However, renewable
similar to that of the gravity separation, a substantial decline resources that undergo biodegradability are an important
in flux was recorded. On the other hand, crude oil was rejected aspect of sustainability. In such situations, an intrinsic bio-
>99% in later cycles (3rd and 4th cycle) for crude oil, which degradability factor of a new engineering material helps in balan-
remained constant for several repetitions. Interestingly, for cing environmental issues associated with disposal after use.
hexane–water feed, rejection was stable to the point ∼98% In our case, we tested membranes for their recyclability (ESI
retaining a substantial amount of permeate flux. It is also Fig. S2†) and reusability after washing in a simple soapy water
evident that the 4th and 5th cycles recovered initial flux over to remove adhered oil contaminants on the membrane
200 L m−2 h−1. Unlike the dead end module, crossflow testing surface. In this way, foam membranes were repeatedly tested
revealed a self-cleaning ability of foam membranes. It is a sig- for their recyclability. In the case of fouled membranes,
nificant phenomenon to note when transmembrane pressure material disposal also happened to be environmentally
is minimal, the capillary pressure prevents the oil from defus- friendly as FM readily undergoes biodegradation. Fig. 6(c)
ing into pores and the crossflow velocity clears the surface, pre- illustrates a photograph where the FM is seen gradually under-
venting scale formation (Fig. 6(a)). This significant going the degradation process. Oil-fouled FM was concealed in
phenomenon adds more value to the membrane life and the soil, and the biodegradation process was monitored con-
long-term stability, maintaining high rejection, which satisfies stantly. After 5 and 10 days, the membrane status clearly
the product water reuse and discharge norms. shows the physical deformation induced by the bio-degra-
Unlike traditional membrane processes, which make use of dation process. More than 50% (w/w) weight loss was recorded
dense or asymmetric micron-scale separating barriers, the after 10 days. From the observations, it is clear that FM readily
present study makes use of foam membranes. It is likely that undergo complete biodegradation process in 25–30 days’ time
separated oil aggregates will accumulate on the membrane without affecting the environment.
developing a blocking layer to a large extent. Moreover, in stable
emulsified wastewater streams, like oil spill samples, suspended
contaminants readily form cakes on the membrane. With the
self-cleaning nature of the foam membrane with optimized
4. Conclusions
crossflow run, the fouling layer formation can be minimized. In summary, the present study demonstrates that microporous
However, at the same time, columnar microstructures in mem- foam membranes have several advantageous properties with
branes could collapse under crossflow pressure generated by respect to their use in oil–water separation. The attractive pro-
the feed pump crossflow velocity. One such experiment was con- perties of foam membranes include natural abundance, less-
ducted to check the surface morphology of the membrane when to-no toxicity, stability under different testing conditions, easy
it repeatedly exposed to an oil–water mixture under pressure. processability and disposability. The biodegradability factor is
Fig. 6(b) gives an SEM image of a fouled membrane. After a significant characteristic of the foam membrane, which
several runs, contaminated oil aggregates accumulated on the makes it an eco-friendly separation medium in comparison to
membrane surface. In such cases, flux decline is inevitable (ESI conventional materials and methods. Over 500 L m−2 h−1 with
Fig. S3†), but it can be minimized with suitable engineering ∼98% pure water is a promising feature of our microporous
adopted to protect membranes from direct flow impact. membrane. FM also works in an advanced crossflow configur-
ation, which opens new avenues to faster water reclamation
processes from large industrial wastewater streams. One of the
prospective focus of using FM is to reclaim water from oil or
gas exploration operations. Oil–water emulsion wastes and oil
sludge are easy to process with an improved rate of the de-
watering process. Therefore, water recovery using a continuous
filtration process and bio-based membranes is an economical
and sustainable solution.
Acknowledgements
CSIR-CSMCRI communication number 056/2014. RM and JPC
Fig. 6 Performance of bio-based foam membranes (a) pure water
gratefully acknowledge DST, New Delhi, Government of India
transport through superhydrophilic (θwater ≈ 0) channels leaving behind
rejected oil (b) SEM image with retained oil deposits on the oleophobic
for financial support (SB/EMEQ-052/2013). SKN gratefully
surface (θwater > 150), (c) biodegraded foam membranes in soil examined acknowledges the DST, Government of India for the DST-
after 5 days and after 10 days (about 50 weight loss was obtained). INSPIRE Fellowship and Research Grant (IFA12-CH-84).
This journal is © The Royal Society of Chemistry 2014 Green Chem., 2014, 16, 4552–4558 | 4557
View Article Online
Notes and references 11 F. Zhang, W. B. Zhang, Z. Shi, D. Wang, J. Jin and L. Jiang,
Adv. Mater., 2013, 25, 4192–4198.
Published on 15 July 2014. Downloaded by Central Salt & Marine Chemicals Research Institute (CSMCRI) on 22/01/2015 08:12:53.
1 S. E. Allan, B. W. Smith and K. A. Anderson, Environ. Sci. 12 Z. Shi, W. Zhang, F. Zhang, X. Liu, D. Wang, J. Jin and
Technol., 2012, 46, 2033–2039. L. Jiang, Adv. Mater., 2013, 25, 2422–2427.
2 C. Pérez, A. Velando, I. Munilla, M. López-Alonso, D. Oro, 13 A. K. Kota, G. Kwon, W. Choi, J. M. Mabry and A. Tuteja,
S. E. Allan, B. W. Smith and K. A. Anderson, Environ. Sci. Nat. Commun., 2012, 3, 1025.
Technol., 2008, 42, 707–713. 14 K. Yoon, K. Kim, X. Wang, D. Fang, B. S. Hsiao and B. Chu,
3 A. M. Bernabeu, D. Rey, B. Rubio, F. Vilas, C. Domínguez, Polymer, 2006, 47, 2434–2441.
J. M. Bayona, J. Albaigés, S. E. Allan, B. W. Smith and 15 W. Zhang, Z. Shi, F. Zhang, X. Liu, J. Jin and L. Jiang, Adv.
K. A. Anderson, Environ. Sci. Technol., 2009, 43, 2470– Mater., 2013, 25, 2071–2076.
2475. 16 Q. Wen, J. Di, L. Jiang, J. Yu and R. Xu, Chem. Sci., 2013, 4,
4 R. H. Carmichael, A. L. Jones, H. K. Patterson, 591–595.
W. C. Walton, A. Pérez-Huerta, E. B. Overton, M. Dailey, 17 R. Meena, A. K. Siddhanta, K. Prasad, B. K. Ramavat,
K. L. Willett, S. E. Allan, B. W. Smith and K. A. Anderson, K. Eswaran, S. Thiruppathi, M. Ganesan, V. A. Mantri and
Environ. Sci. Technol., 2012, 46, 12787–12795. P. V. S. Rao, Carbohydr. Polym., 2007, 69, 179–188.
5 J. Rivas, A. R. Prazeres and F. Carvalho, J. Agric. Food 18 Q. L. Q. Feng, J. Mater. Sci. Mater. Med., 2006, 17, 1349–
Chem., 2011, 59, 2511–2517. 1356.
6 F. J. Rivas, O. Gimeno, J. R. Portela, E. M. de la Ossa and 19 R. Touyama, K. Inoue, Y. Takeda, M. Yatsuzuka,
F. J. Beltrán, Ind. Eng. Chem. Res., 2001, 40, 3670–3674. T. Ikumoto, N. Moritome, T. Shingu, T. Yokoi and
7 A. Asatekin and A. M. Mayes, Environ. Sci. Technol., 2009, H. Intuye, Chem. Pharm. Bull., 1994, 42, 1571–1578.
43, 4487–4492. 20 L.-W. Xia, R. Xie, X.-J. Ju, W. Wang, Q. Chen and L.-Y. Chu,
8 T. J. Crone and M. Tolstoy, Science, 2010, 330, 634. Nat. Commun., 2013, 4, 2226.
9 J. H. Bannock, T. W. Phillips, A. M. Nightingale and 21 D. Saravanan, T. Gomathi and P. N. Sudha, Arch. Appl. Sci.
J. C. deMello, Anal. Methods, 2013, 5, 4991–4998. Res., 2011, 3, 342–350.
10 Y. Zhu, D. Wang, L. Jiang and J. Jin, NPG Asia Mater., 2014, 22 M. U. Chhatbar, R. Meena, K. Prasad, D. R. Chejara and
6, e101. A. K. Siddhanta, Carbohydr. Res., 2011, 346, 527–533.
4558 | Green Chem., 2014, 16, 4552–4558 This journal is © The Royal Society of Chemistry 2014