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Article
Chitosan-Based Aerogel Membrane for
Robust Oil-in-Water Emulsion Separation
Jai Prakash Chaudhary, Nilesh Vadodariya, Nataraj Sanna Kotrappanavar, and Ramavatar Meena
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.5b08705 • Publication Date (Web): 20 Oct 2015
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Page 1 of 7 ACS Applied Materials & Interfaces

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Chitosan-Based Aerogel Membrane for Robust Oil-in-Water Emulsion Separation
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Jai Prakash Chaudhary,a,c Nilesh Vadodariya,a,c Sanna Kotrappanavar Nataraj,b,c* Ramavatar Meenaa,c*
10 a
Scale-Up & Process Engineering Unit Discipline, CSIR-Central Salt & Marine Chemicals Research Institute, G. B. Marg,
11 Bhavnagar-364002, Gujarat, India.
12 b
RO-Division, CSIR-Central Salt & Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-364002, Gujarat, India.
13 c
14 AcSIR-Central Salt and Marine Chemicals Research Institute, G. B. Marg,
15 Bhavnagar-364002, Gujarat, India
16 E-mail: rmeena@csmcri.org; ramavatar73@yahoo.com
17
Fax: +91-278-2567562; Tel: +91-278-2567760
18
19 E-mail: sknata@gmail.com, sknataraj@csmcri.org
20 KEYWORDS. Biopolymer, emulsion, wastewater, aerogel membrane, oil-water separation
21
22 ABSTRACT: Here we demonstrate, direct recovery of water from stable emulsion waste using aerogel membrane. Chitosan based
23 gel was transformed into highly porous aerogel membrane using bio-origin genipin as crosslinking agent. Aerogel membranes were
24 characterized for their morphology using SEM, chemical composition by FTIR and solid-UV. Further, aerogel was tested for re-
25 covery of high quality water from oil spill sample collected from ship breaking yard. High quality (with >99% purity) water recov-
26 ered with flux rate of >600 L.m-2.h-1.bar-1. After repeated use aerogel membranes were tested for greener disposal possibilities by
27 biodegrading membrane in soil.
28
29
30 INTRODUCTION separation. Therefore, present study explores use of highly
31 porous polysaccharide chitosan based aerogel membrane for
Oil-in-water or water-in-oil emulsions are stable liq-
32 uid/liquid systems which cause serious environmental problem recovering water from oil-spill and stable emulsions.
33 in absence of proper separation techniques. 1-3 Oil-water emul- Macroporous aerogel was prepared using agarose and chitosan
34 sions generally classified in to 3 categories depending on their mixtures. Here agarose used as both pore formation agent as
35 stability namely, loose, medium and tight emulsions. Loose well as surface coating on highly cross-linked chitosan net-
36 and medium emulsions can be easily phase separated. Howev- work. This unique feature helps in robust selection of water
37 er, a tight emulsion cause serious problems and requires prop- from stable emulsions. In our previous study, 13 we demon-
38 er demulsification agent or method to break the emulsion. strated gelatin as minor constituent for preparing superhydro-
39 Large quantities of industrial emulsion wastes discharged to philic aerogel membrane, but for sustainable and large scale
40 water bodies pose greater threat to aquatic life in particular applications stable aerogel filter is vital.
41 causing rapid increase in the chemical oxygen demand (COD) Therefore, here highly cross-linked chitosan acts as
42 and biological oxygen demand (BOD).4 Demulsifiers have support network along with inducing hydrophilicity to aerogel.
43 been popular choice among many to safely separate oil-water As prepared membrane was tested for selective water separa-
44 emulsions. But in the recent past, there have been several at- tion from bio-diesel/water emulsion, crude vegetable oil/water
tempts made to selectively separate water from oil or oil from emulsion and highly contaminated oil spill wastewater. For
45
water using different materials.5-7 Membrane based processes sustainable applications, membranes were tested under cross-
46
like reverse osmosis (RO) and ultrafiltration (UF) in combina- flow filtration mode. In all cases, permeate water purity was
47 tion with demulsifiers have been tested under different condi- >99 % at high water flux >600 L.m-2.h-1.
48 tions for removal of oil from emulsion wastewater. 8-10 In the EXPERIMENTAL SECTION
49 last two years, more advanced materials have emerged in dif-
50 Materials
ferent form like aerogels,11,12 foam membranes,13 polysaccha-
51 ride agents,14 surface modified fabrics and inorganic meshes Hydrophilic polysaccharide agarose was extracted
52 for successful separation of oil/water mixtures. 15-17 Unique 3D from red seaweed Gracilaria dura following the method re-
53 network of hydrophilic aerogels preferably select water over ported in literature.19,20 Chitosan was purchased from Sigma
54 oil, similarly transforming surface to hydrophobic, oil was Aldrich and Genipin was purchased from Challenge Bioprod-
55 preferably separated from water. These new class of materials ucts Co. Ltd. (Taiwan). And all other chemicals were used as
56 have shown excellent separation properties because of their received without further purification. Biodiesel and crude oil
large surface area, high porosity and can be easily custom were procured from our institute pilot plant, oil-spill collected
57
58 made to fit the final application.18 However, bio-based aero- from ship breaking yard, Alang, Gujarat and used without any
gels owing distinctive features like sustainability and biode- further purification. Further oil:water emulsions were also
59 prepared in 20:80 v/v ratio of simply by vigorous stirring.
gradable aspects in addition to super-hydrophilicity and high
60
surface area make them better choice for oil-water emulsion
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Preparation of aerogel membrane sion feed was continuously circulated using booster pump
1 Different compositions of membranes were prepared (KEMFLOW) with nominal flow rate of 1.8 LPM capable of
2 by changing the total polymer concentration ranging from 0.5 maintaining pressure between 0–10 bar. Restricting needle
3 % to 2 % w/v keeping Agarose: Chitosan ratio constant (9: 1 valves were provided in the membrane kit to control the flow
4 w/w) in all formulations, and tested for their oil/water separa- rates. The permeate purity (% rejection of oil) and flux for
5 tion performances. Membranes were designated in abbrevia- aerogel membrane were calculated using following equations;
6 tion as follows, chitosan as CS, agarose as Agr, genipin as G, 𝑉
𝐽𝑛 = 𝐴(𝑡 …………………………..(1)
7 blend of chitosan-agarose as CS-Agr and genipin crosslinked 0 −𝑡𝑛 )
8 aerogel as CS-Agr-G. To obtained different membranes 450 to
9 900 mg agarose was taken in separate beakers having 75 ml Where, Jn is flux (L.m-2.h-1), V is volume of permeate, A is
10 distilled water and solubilized by autoclaving it at 120 oC for effective area of the membrane and to at zero time and at in-
11 15 min. In another sets of beakers 50 to 100 mg chitosan was terval n, respectively.
12 dissolved in 25 ml of 0.05M acetic acid (Figure 1). Then chi- Considering water as rich phase in permeate, infrared (IR)
13 tosan solution was added to the viscous agarose solution under spectroscopy has been used to quantify the amount of oil dif-
vigorous stirring conditions for 10 min at 80 oC followed by fused with permeate water. Prior to permeate sample analysis,
14
addition of genipin (10-40 mg in 0.5 ml methanol) with con- we calibrated standard curve for different concentrations of
15 tinuous stirring at 80 oC and gradually cooled to room temper-
16 oil-in-water. Six standard solutions over the range of 1 to 100
ature to form hydrogel. After 5-10 min, the colour of whole mg.L-1 oil-in-water were prepared for stable emulsion using
17 solution starts changing from transparent solution to blue col- sonication bath. Further, these samples were subjected to
18 our due to the cross linking and resulting hydrogel was left for FTIR analysis. Established calibration range fitted well with
19 2-3 days at room (25 oC) temperature for complete crosslink- linearity and accuracy were observed with a correlation coef-
20 ing. After that each gel was cut to 0.4 mm thick slices and ficient (R2=0.99325) and a standard error of 0.2143 mg/mL
21 lyophilized to obtained aerogel samples for separation applica- was obtained. Therefore, % rejection of oil was calculated
22 tions.13 using equation;
23 The best result was obtained with aerogel obtained ∁𝑓 − ∁𝑝
24 with 1 % w/v of total polymer concentration (Agr: CS = 9: 1 %𝑅 =( ) x100……..…………………(2)
∁𝑝
25 w/w), and was considered optimum polymer concentration in
26 this study. Flux (J) of permeate and % rejection oil in perme- Where, Cf and Cp are the concentration of feed and permeate
27 ate was calculated as method reported in our previous paper.13 solutions, respectively.
28 Methods Results and Discussions
29 Agarose solutions were prepared by Autoclaving it
30 using Autoclave ES-315 (TOMY SEIKO Co., Ltd, Japan).
31 Further, cross-linked gel were subjected to Lyophilisation
32 using VirTis Benchtop, Freeze dryer, United States for getting
33 final aerogel membranes. FTIR spectra were recorded on a
34 Perkin-Elmer design instrument (Spectrum GX, USA). The
35 aerogels membrane were analysed for their surface morpholo-
36 gy and pore characteristics for both control and cross-linked
37 chitosan membranes using scanning electron microscopy
38 (SEM) on a Carl-Zeiss Leo VP 1430 instrument (Oxford
39 INCA). Thermogravimetric analysis (TGA) was carried out
40 using Mettler Toledo Thermal Analyzer, (TGA/SDTA 851e,
Switzerland). TGA was carried out using 6 mg of each sample
41
under N2 atmosphere with a heating rate of 10o/min. The solid
42 state UV-vis spectra were measured using Shimadzu UV-
43 3101PC spectrophotometer (JAPAN). 13C CP MASS spectra
44 of each constituent were recorded on a Bruker Avance-II 500
45 (Ultra Shield, Switzerland) spectrometer under ambient condi-
46 tion.
47 Membrane testing
48
The aerogel membranes were tested for their separa-
49
tion performances using simple funnel with membrane sitting
50 in neck to selectively passage water. Initially 2 different kind
51 of emulsions namely, crude bio-diesel/water and oil spill
52 wastewater were tested. No dye or artificial colour was used to
53 distinguish feed samples (either to water or to oil). As emul-
54 sions were stable before pouring to container funnel and time Figure 1. Schematics of preparing chitosan-based aerogel mem-
55 was recorded to separate water from 20:80 (v/v) oil/water brane (a) control, (b) genipin cross-linked chitosan aerogel and (c)
56 emulsion. Subsequently, both permeation rate and purity was genipin-chitosan cross-linked chemical structure with inner walls
57 evaluated. To evaluate compression breaking, recyclability of CS linked with agarose in H-bonding.
58 and large scale continuous operations, membranes were tested
59 in crossflow conditions. Membranes were fitted in crossflow The preparation procedure for superhydrophilic aga-
60 membrane testing unit comprising of hollow chamber. Emul- rose inner wall coated CS aerogel membrane has shown sche-

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matically in Figure 1. Chitosan is one of the abundant natural the product.21 Presence of additional characteristics agarose
1 resource extracted from the shells of shrimp, lobster, and and chitosan peaks in FTIR spectrum of crosslinked CS-Agr-
2 crabs. CS is also fibrous in nature that can be used in different G further confirms that the main backbone of pristine agarose
3 forms upon chemical and physical modification, and can be and chitosan remained intact during modification.
4 chemically cross-linked using –NH2 functionality of CS. Fur- The main noticeable change appeared in the shift of
5 ther, CS can also be transformed in to a stable scaffold-like broader Agr stretching peak (-OH) at ~3438 cm-1 upon blend-
6 structure by controlling degree of crosslinking. To make large ing with CS (~3435 cm-1) to ~3400 cm-1 in CS-Agr. This re-
7 pore size aerogel membrane, agarose used as gelling agent mained unchanged upon genipin crosslinking in CS-Agr-G.
8 which also helped in creating highly porous aerogel mem- Therefore, hydroxyl (-OH) groups present in agarose make
9 brane. Interestingly, agarose also played in enhancing hydro- hydrogen bonding interaction with N lone pair of the amide
philic property by interacting with chitosan through H- group of chitosan resulting in columnar structure in which CS
10
bonding during lyophilisation. Proposed structure in Figure walls are coated with Agr. Crosslinking of CS was further
11 1(c) shows genipin readily crosslinks chitosan at 80 oC, while confirmed using solid UV spectroscopy as shown in Figure
12 agarose undergoes H-bonding interaction with –OH of chi- 2(b). Pristine genipin exhibits sharp characteristic peak at 240
13 tosan making it stable gel at room temperature. To confirm CS nm, whereas none of the control CS, Agr or blend CS-Agr
14 crosslinking and CS-Agr interactions in aerogel membrane shown any recognizable peaks. But, when genipin added to
15 FTIR and solid-UV measurements on both control CS-Agr blend gel (CS-Agr-G), spectra shift sharply for characteristic
16 and genipin cross-linked CS-Agr were analysed. In all cases, genipin peak to 282 nm with much less intensity. During the
17 IR spectrum of individual constitutes CS, Agr and genipin process, a significant change also happens with the appear-
18 were also recorded to highlight changes. ance of additional peak at 600 nm. This confirms extended
19 conjugation of genipin crosslinking in CS matrix which in-
20 duces dark green colour to aerogel membrane.13,22 Figure 2
21 (c&d) shows SEM morphologies of large pore size CS-based
22 aerogel membrane at different magnifications, which clearly
23 indicateds pore size distribution was in macroporous range of
24 40-50 µm. Close view of SEM images reveals that lyophilisa-
tion process induced well-ordered pattern to CS membrane.
25
Formation of large column-like pore structure may also be
26 attributed to uniform size CS polymer chains which trapped
27 agarose gel mass in it.
28
29 Thermogravimetric (TGA) was used to determine na-
30 ture of membrane transformation and their thermal stability.
31 TGA results (see, Figure S2(a-d)) of the blend (Agr-CS) as
32 well as genipin crosslinked blend (Agr-CS-G) prepared in the
33 presence of crosslinking agent showed the high thermal stabil-
34 ity in comparison to pristine constituents. The minimum resid-
35 ual mass of 20.53%, 25.05% and ~31.21% was obtained for
36 Agr, CS and CS-Agr blends, respectively. However, genipin
37 crosslinked blend (Agr-CS-G) retained as high as 41.08%
38 residual mass at 599.5oC. Therefore, it directly implies the
rigid network as a result of genipin crosslinking in aerogel
39
membranes. As shown mass loss was higher in control poly-
40
mers and was maximum for agarose. The blend Agr-CS shows
41 less mass loss compared to control polymers indicates network
42 Figure 2. (a) FTIR spectra of agarose-chitosan (Agr-CS-G) aero- stability may be due to the hydrogel bonding between Agr–
43 gel crosslinked using genipin, and (b) Solid UV spectra of pristine OH and lone pair –NH2 of CS. The crosslinked blend shows
44 and cross-linked CS-Agarose aerogel membranes and their pre- the lowest mass loss and greatest thermal stability may be the
45 cursors, (c&d) SEM images of different magnifications Genipin result of the formation of strong covalent and hydrogen bond-
46 cross-linked chitosan-agarose aerogel membrane, and (e) sche-
ing during this process. Based on FTIR, solid UV and SEM
matics of proposed porous aerogel membrane formation mecha-
47 nism.
analytical evidence it can be assumed that CS-Agr gel for-
48 mation is robust and following mechanism can be proposed
49 Figure 2(a) shows FTIR analysis of all constituents for aerogel membrane formation as shown in Figure 2(e).
50 where agarose exhibited characteristics peaks at 932 cm-1 (due Firstly, when CS and Agr mixed together limited interaction
51 to 3, 6-anhydrogalactose linkage), 1160 and 1076 cm-1.19,20 of CS with Agr forms island clusters where mass of agarose
52 Chitosan exhibited characteristic stretching vibrations at 1645 covered with CS polymer boundaries gel. Further, when cross-
53 cm-1 (C=O stretching vibration), and additional peaks between linking agent genipin added to CS-Agr mixture inter and intra-
1000-1100 cm-1 were attributed to C-O and C-N stretching chain crosslinking of CS initiates forming dense column-like
54
vibrations. Genipin exhibited characteristics band at 1443 walls holding Agr gel mass inside. When gel undergoes lyoph-
55 cm−1 was assigned to a ring stretching mode in the genipin ilisation water trapped in agarose gets crystalizes pushing aga-
56 molecule. While appearance of new band at 1415 cm-1 in rose to CS walls. So, it leads to confirm that super hydrophilic
57 product (Agr-CS-G) after genipin crosslinking indicated pres- CS with macropore in which Agr thin-layer surrounded by
58 ence of ring stretching of heterocyclic amine. The shoulder at stable CS walls with inter-wall crosslinking used for selective
59 1641 cm-1 represents the stretching of C=O also appeared in separation from oil-water emulsions.
60
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Aerogel membranes further characterized for their oils, respectively. Whereas, in both permeates all significant
1 thermal stability and swelling properties both in pure water peaks disappeared. The % rejection of oil was calculated us-
2 and oil/water emulsion to determine best membrane composi- ing standard plot for different concentration oil-in-water
3 tion. Membrane with composition of 0.04 wt% crosslinking emulsion, which for both case noted to be >99%.
4 agent genipin showed moderate swelling (~60 %) in both
5 pure water and emulsion (see Figure. S1). This independent
6 swelling behavior for different feed condition is an encourag-
7 ing property as it indicates affinity of membrane surface for
8 selective absorption and subsequent permeation of water.
9 Pre-wetted membrane of 2.0 cm diameter was fixed
in the neck of a funnel to make it filtration set-up. Figure 3(a)
10
shows the membrane used to filter biodiesel emulsion and
11 highly contaminated oil-spill sample (Figure 3b&c). Time
12 dependent selective separation of water from oil was evaluat-
13 ed. Figure 3(b1&b2) represent biodiesel emulsion before and
14 after oil water separation at the rate of 213 L.m-2.h-1. Similar-
15 ly, Figure 3(c1&c2) shows the separation pattern of oil-spill,
16 interestingly much faster rate of 284 L.m-2.h-1. Quality of
17 permeate water analyzed for separation efficiency using FTIR
18 measurements. Figures 3(d&e) shows characterization of feed
19 stable emulsion and permeate and pure water along with con-
20 trol pure oil for both biodiesel and oil-spill, respectively.
21
22 Figure 4. (a&b) crossflow membrane testing unit used for Crude
23 biodiesel-based emulsion separation where (c) schematic depicts
membrane and permeate chamber. (d) FTIR analysis of emulsion
24
feed and permeates collected at different time intervals in a long
25 term run, and (e) give % oil rejection and flux (L.m-2.h-1.bar-1)
26 trend for different oil/water emulsions.
27 Further, large scale continuous flow test is an essen-
28 tial to evaluate membrane stability and practical application.
29 Crossflow membrane testing unit with feed chamber and spe-
30 cially made membrane/permeate chamber shown schematical-
31 ly in Figure 4(a,b&c), respectively. Unlike many reported
32 articles, we tested CS-aerogel membranes vigorously under
33 crossflow module for 8 hours collecting permeate samples in
34 regular time interval for analysis both emulsions (crude bio-
35 diesel and oil-spill) were tested. Figure 4(d) gives FTIR anal-
ysis of feed and permeates at different time intervals, which
36
reveals significant rejection of oil in permeate. It is evident
37
that over 650 L.m-2.h-1.bar-1 fluxes yielded with ~99 % pure
38 water Figure 4(e).
39 It is also important that the flux and rejections were
40 consistent for several hour of continuous and repeated run.
41 One of the advantages using CS-aerogel membrane is post
42 emulsion separation, membrane surface can be easily regen-
43 erated by simple washing. Membrane were also tested verti-
44 cally to examine the fouling and extent of membrane defor-
45 mation Figure 5(a). Extent of membrane deformation under
46 crossflow pump pressure is evident from Figure 5(b) before
47 and after test run. SEM images in Figure 5(c&d) also reveals
48 the extent of deformation clearly. Under feed flow pressure
49 large pores were seem completely collapsed.
50
However, membranes regains significant physical characteris-
51
Figure 3. (a) Photograph of coin size aerogel membrane used to tics after surface regeneration process by washing in DI water
52
separate (b) bio-diesel/water emulsion (c) oil-spill wastewater (Figure S4(a)), which was further used repeatedly. Surface
53 regenerated membrane retained substantial flux of water from
emulsion collected from ship breaking yard (b1 & b2) bio-
54 diesel/water emulsion before and after separation and (c1 & c2) contaminated emulsion (Figure S4(b)). For being sustainable
55 oil-spill wastewater emulsion before and after separation. (d) & and green, material after use should undergo biodegradation.
56 (e) gives FTIR analysis of feed emulsion and pure oil samples (& We tested CS-based aerogel membrane after several cycle of
57 received oil spill) and permeates water characterized for their use, keeping used membrane in soil for natural degradation.
58 purity. Figure 5(e) gives photographs of aerogel membrane undergo-
59 Emulsion and pure oil samples have characteristic peaks at ing biodegradation at different time interval. Under normal
60 1745 and 2930 cm-1 for C=O of esters and C-H stretching of soil conditions membrane biodegraded considerably in 25
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days’ time. Further, after 35 days of observation membrane

1 lost 60-70% original mass. For complete green process it is
2 significant that using bio-origin to biodegradation a material Acknowledgements
3 completes the life cycle. CSIR-CSMCRI Communication No. 159/2015.
4 SKN gratefully acknowledges the DST, Government of India
5 for the DST-INSPIRE Fellowship and Research Grant
6 (IFA12-CH-84). RM, JPC and Nilesh gratefully acknowledge
7 DST (SB/EMEQ-052/2013) and CSIR, New Delhi, Govern-
8 ment of India for financial support (CSC0130).
9
Notes and references
10
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10 Chitosan-Based Aerogel Membrane for Robust Oil-in-Water Emulsion Separation
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