ISSN- 2394-5125 VOL 7, ISSUE 12, 2020 REMOVAL OF CHROMIUM ION USING NANOCELLULOSE BASED ADSORBENT

Rekha Goswami1, Abhilasha Mishra2, Neha Bhatt3, Pratibha Naithani4

1,4Department of Environmental Science, Graphic Era (deemed to be University) 1Department of Environmental Science, Graphic Era Hill University 2,3Department of Chemistry, Graphic Era (deemed to be University)

E-mail: [email protected]

Received: 14 March 2020 Revised and Accepted: 8 July 2020

ABSTRACT: Heavy metal pollution is emerging as one of the most serious problems possesses various health hazards as well as environmental degradation. In this regards nanotechnology is found to be most effective strategy. India is agriculture based country in which yearly tones of agriculture byproduct is discarded with least management practices. In present study sugarcane baggase is used as a raw material for cellulose nanocrystal isolation by adopting alkali pretreatment followed by acid hydrolysis technique. Nanocellulose composite beads were prepared by using sodium alginate and charcoal. The removal of chromium ion by prepared nanocomposite beads was studied by means of column study. To assess the structural characteristics of prepared nanocellulose FTIR and XRD analysis were carried out. The IR spectra showed characteristic peaks of cellulose structure and XRD analysis confirms the crystalline behavior of prepared cellulose nanocrystals. Amount of cellulose nanocrystals was found to have a significant effect of chromium ion adsorption. It was also observed that on increasing contact time initially the removal rate was increase but later on after 50 minutes it was showing a decreased removal rate.

KEYWORDS: Heavy metals, FTIR, XRD, Sugarcane baggase

I. INTRODUCTION Potable water is the utmost requirement for today generation. Due to over exploitation and mismanagement of the water resources, water pollution etc results in origination of water scarcity. So that wastewater treatment is seems to be necessary to make the wastewater in some usable form. Heavy metal pollution is the presence of metallic chemical elements having elevated density and toxic at very less quantity [1]. Many industrial fields are responsible for the upsurge of the heavy metals in the water bodies such as leather, electroplating, textile industries and nuclear power plant results in deteriorating the water quality [2]. Chromium ion present in few oxidation state, among them chromium (VI) is hazardous in nature [4, 5, 6]. Its contact cause fatal diseases like digestive tract and lung cancer, vomiting, haemorrhage which affects human’s life [3].In general chemical oxidation, chemical precipitation, ion exchange, electrodialysis techniques are adopted for the amputation of the heavy metals [7]. Besides all method, adsorption is one of the highly used techniques for wastewater treatment. On the other side these techniques have some constraint such as high O & M cost, sludge management and its proper disposal system, less competent etc. [8]. So in view to overcome these problem to some extent nanotechnology gain significant attention in past few decades towards various environmental remediation used as an adsorbent, filter membrane, flocculants due to its nanosize dimension, high surface area, hydrophilicity behavior towards contaminant. For this purpose natural polymers obtained from plant resources are most studied, found to be more efficient. In this study sugarcane baggase is used as the source of nanomaterials for the extraction of cellulose known to be a natural polymer and also present in huge amount as agricultural waste product with low price. [9]

Cellulose is semicrystalline in nature containing anhydroglucose units (AGUs) binded with β-1, 4-glycosidic bonds. Cellulose is known as the renewable organic matter found extensively in variety of plants materials such as wood, sisal, hemp, flax, coconut husk [10]. empty palm oil fruit bunch [11], sour sop seeds [12] modified cassava, cassava fibre [13]; coconut shell[14] and Wolffia globosa (duck weed) [15].; animal like tunicates which generate cellulose in pure form with high degree of crystallinity additionally it having high aspect ratio 60–70 and high specific surface area ranges 150–170m2 g−1 [16–18]. As well as in various type of algae belongs to Valoniaceae family (Valonia), Desmid green alga, Micrasterias rotate, Coldophora, Boerogesenia are also used [19-22]. The presence of cellulose content is high in plants material as compared to the other sources. [23].

4148

ISSN- 2394-5125 VOL 7, ISSUE 12, 2020 On the basis of Technical Association of Pulp and Paper Industry (TAPPI) the nanocellulose is basically classified into two subgroup i.e. cellulose nanocrystal and cellulose nanofibers in terms of its size, dimension and morphology shown in fig.1. Generally nanofibril are extracted by mechanical process possess diameter ranging from 10-100 nm in contrast cellulose nanocrystal have high degree of crystalline nature due to the presence of elongated rod like region [24]. Range of techniques is used to produced nanocellulose which generally ranging from 10 nm to 350 nm having high surface area comparatively to normal cellulose. For the isolation of cellulose nanocrystal hydrolysis is one of the main method, in which different type of acids are to be used. Generally sulphuric acid is highly recommended for the chemical disintegration of cellulose into nanocrystal form [25]. Many researchers used organic and mineral acids [26,27].There are some major factors such as contact time, acid/pulp ratio, acid strength and temperature which play a crucial role during hydrolysis reaction. [28]. On the other hand various mechanical methods such as grinding [29], homogenization [30], microfluidizer [31]; Simple Ball Milling [32] and ultrasonication [33] adopted to produce cellulose nanofibrils. During isolation process mechanical forces exerts results in breakage of the interfibrillar linkage between the molecules. The resultant nanofibers attain length and width in nanodimension [34]. Cryocrushing is also used as an alternative method for the production of nanodimension fibers. [35]. In this study we evaluate the potential of the beads contains different proportion of cellulose nanocrystal towards the removal of chromium ion from the aqueous solution. The advancement in the nanocellulose is highly focused research area over past few decades due to its high potentiality and stiff behavior as well as eco friendly in nature [36].

Fig.1: Structure of Nanocellulose

II. MATERIALS AND METHODS Collection and preparation of the sample Agricultural waste product i.e. sugarcane baggase was used as cellulose source during study. Sodium hydroxide, Sulphuric acid, Potassium dichromate, diphenyl carbazide as indicator, Sodium alginate, Activated charcoal, calcium chloride (cross linking agent) was purchased from Merck and Rankem. All chemicals were used without any distillation and purification further and distilled water was used during analysis.

Pretreatment Grinding Raw sugarcane baggase was firstly chopped into small pieces manually and then grind into the homogenous mixture. For the isolation of cellulose size (75µ, 150 µ, 300µ, 425µ) sieve shaker was used. In this study 150 µ size nanocellulose was used.

Bleaching After isolation of different cellulose dimension the mixture was bleached using sodium hypochlorite as bleaching agent. About 3.0 gm of sodium hypochlorite was taken in 250 ml double distilled water and stirred for 6 hours at 45oC to eliminate lignin, hemicelluloses and any wax remaining from the raw cellulose i.e. sugarcane baggase. After completion of process the residue was washed with distilled water until becomes neutralize and kept for drying at room temperature for 2 days.

Chemical Treatment Acid Hydrolysis The dry bleached sample was hydrolyzed in 2% sulphuric acid stirred for 1 hours at 50oC. Resulting mixture was cooled at room temperature. After hydrolysis the resultant suspension was centrifuged at 6500 rpm for 30 minutes. After 5 to 6 wash with distilled water centrifugation process was stopped to neutralize the sample. Overall preparation steps are shown in fig.2.

4149

ISSN- 2394-5125 VOL 7, ISSUE 12, 2020

Fig. 2: Overall preparation process of Cellulose Nanocrystal

Preparation of Nanocellulose beads Ionotrophic gelation method was adopted for the formation of the nanocellulose composite beads. The homogenized solution of 20 ml contain Sodium alginate (0.3 g), Charcoal (0.3 g), and varying amount of nanocellulose i.e. 1.0 gm, 1.5 gm, 2.0 gm and 2.0 gm. The resultant solution was introduced into 2% calcium chloride solution by means of syringe in drop wise manner to make the composite beads. To remove the excess amount of CaCl2 from the beads, it was kept for 24 hours in distilled water and then washed. Fig. 3 showing preparation method and final image of nanocomposite beads.

Cellulose Nanocrystal + Crosslink Calcium Chloride Sodium Alginate + Charcoal (Beads Formed) (Homogenous Suspension)

Fig.3: Schematic of beads formations

Characterization To characterize the resulted cellulose nanocrystal following study was done: Fourier transform Infrared spectroscopy (FTIR) The structural characterization of resulted cellulose nanocrystal was done by recording FTIR spectra using FTIR instrument model Perkin Elmer spectrum two.

X Ray diffraction (XRD) To check the crystalline behaviour of the cellulose nanocrystal this technique was adopted by using instrument model 18KWCu-rotating anode Rigaku.

Column Study Sintered disc column was used during study period. Column was filled with nanocomposite beads up to 3 cm shown at fig.4. Approx 20 ml chromium solution of 0.1% was poured into the column at fixed flow rate of 1ml/min. The sample of metal solution was collected at different time intervals and analyzed using UV-Vis spectrophotometer at wavelength of 540nm.

The amount of chromium ion adsorbed on the beads was calculated by the using mass balance equation.

Where,Adsorbed Chromium Ion Amount (mg/g) = (Ci-Cf) V (1) Ci and Cf = initial and final concentrations (mg dm - 3 ) of m potassium dichromate solution, respectively, V = volume of metal ion solution m = weight of swollen beads taken as adsorbent.

4150

ISSN- 2394-5125 VOL 7, ISSUE 12, 2020

Fig.4: Column study of chromium ion adsorption

III. RESULT AND DISCUSSION Characterization

The characterictics of the isolated cellulose nanocrystal was done by techniques as follows :

FTIR This study was mainly done to detect the functional group availabilty in the isolated cellulose nanocrystal. Refers to fig.5 C-O linkages of two cellulosic units shows the peak at around 1191 cm-1 of the FTIR absorption band. C– O–C stretching vibration of β-(1-4)-glycosidic linkages is at 895 cm-1 and reffered as ―amorphous‖ absorption band. The broad band in the 3600-3100 cm-1 region is due to the OH- stretching vibration, OH gives peak at 3133 cm-1 and showing hydrogen bonds. It may be also due to bound water OH to the sample and OH at 1649 cm-1 also represents cellulose IR spectra. The C–H stretching vibration can be seen at near 2902 cm-1 . -1 The FTIR absorption band at 1317 cm , is due to symmetric CH 2 bending vibration. This band is also known as the ―crystallinity band‖. It is showing some crystalline nature of cellulose. The adsorption bands which are very low in intensity may be neglected.

4151

ISSN- 2394-5125 VOL 7, ISSUE 12, 2020

Fig.5: FTIR study of nanocellulose isolated after acid hydrolysis

XRD To study the crystalline behavior of the isolated cellulose nanocrystal by acid hydrolysed X-Ray Diffraction technique is adopted. Pure cellulose contain amorphous as well as crystalline region; in which amorphous region is easily distorted by hydrolysis process. Previous literature [37] showed that on increasing the acid concentration the crystalline behavior of the nanocellulose was also affected. In this study 2% acid concentration was used showing high crystalline behavior of the resulted cellulose nanocrystal depicted in fig.6 below.

N

1.6

1.4

1.2

1.0

0.8 intensity

0.6

0.4

0.2 0 50 100 2Theta

Fig.6: XRD study of cellulose nanocrystal isolated from acid hydrolysis

Contact time effect in removal rate During adsorption study the effect of the contact time was analyzed and it was found that on increasing the contact time duration of the nanocomposite beads the removal rate of the chromium ion was increased but at some extent the removal efficiency gets constant. It may be due to saturation of the available binding site on the beads surface. The variation in the removal rate of the chromium ion is shown in fig.7 below.

4152

ISSN- 2394-5125 VOL 7, ISSUE 12, 2020

100.0

90.0 Beads without CNC 80.0 70.0 Beads with 1.0 gm CNC 60.0 Beads with 1.5 gm CNC 50.0 Beads with 2.0 gm CNC 40.0 30.0 Beads with 2.5 gm CNC

Removal (%) Rate Removal 20.0 0 20 40 60 80 Contact Time (min)

Fig.7: Variation in removal efficiency with contact time during adsorption

Effect of bead composition Variation in the composition of the nanocomposite beads was also analyzed during study period. It was observed that change in nanocomposite beads composition show significant variation on the adsorption of the chromium ions due to increased active site availability. In this study the amount of cellulose nanocrystal was varied from 1.0 to 2.5 g in the composition of beads and the observed results are shown in fig.8. Initially the removal rate was increased on increasing CNC but after adding 2.0 gm of CNC the removal rate was found to decrease. It is due to the fact that on increasing the nanocellulose quantity into the composition mixture the active site also increases consequently increases the removal rate. However, on increasing the nanocellulose content the beads become compact and hindered the diffusion rate result in low removal efficiency.

100 96 90 80 87 72 60 50 40

20 Removal Removal Rate(%) 0 1.0 1.5 2.0 2.5 (Alginate + (Alginate + Charcoal+ CNC) Beads Charcoal) CNC Concentration Beads without CNC Concentration (gm)

Fig.8: Removal rate variation with varying CNC concentration

IV. CONCLUSION In this study sugarcane baggase has been shown that it act as an effective adsorbent for the removal of heavy metals. Charcoal is one of the known ideal adsorbent used for the contamination removal purpose but on adding cellulose nanocrystal further, it enhances efficiency showing desirable results in waste water quality. The adsorbate get the effective binding site for maximum 50 min after which due to desorption the binding site is not available showing a constant removal rate. It was concluded that the increasing quantity of nanocellulose also affect the removal efficiency of the nanocellulose composite beads. Sugarcane baggase is cost effective in nature available in easy manner and found to be efficient for heavy metal removal.

4153

ISSN- 2394-5125 VOL 7, ISSUE 12, 2020 CONFLICT OF INTEREST No conflict of interest is declared by the authors.

V. REFERENCES

[1] Bediako JK, Wei W, Kim S, Yun YS. Removal of heavy metals from aqueous phases using chemically modified waste Lyocell fiber. J Hazard Mater 2015 Dec 15; 299:550-61. [2] Rao KS, Mohapatra M, Anand S, Venkateswarlu P. Review on cadmium removal from aqueous solutions. Int J Eng Sci Technol 2010; 2(7). [3] Mohanty K, Jha M, Meikap BC, Biswas MN. Removal of chromium (VI) from dilute aqueous solutions by activated carbon developed from Terminalia arjuna nuts activated with zinc chloride. Chem Eng Sci 2005 Jun 1; 60(11):3049-59. [4] Mohan D, Pittman Jr CU. Activated carbons and low cost adsorbents for remediation of tri-and hexavalent chromium from water. J Hazard Mater 2006 Sep 21;137(2):762-811. [5] Mohan D, Pittman Jr CU. Arsenic removal from water/wastewater using adsorbents—a critical review. J Hazard Mater 2007 Apr 2;142(1-2):1-53. [6] Al-Othman ZA, Ali R, Naushad M. Hexavalent chromium removal from aqueous medium by activated carbon prepared from peanut shell: adsorption kinetics, equilibrium and thermodynamic studies. Chem Eng J 2012 Mar 1;184:238-47. [7] Fu F, Wang Q. Removal of heavy metal ions from wastewaters: a review. J Environ Manage 2011 Mar 1;92(3):407-18. [8] Agarwal M, Singh K. Heavy metal removal from wastewater using various adsorbents: a review. J. Water Reuse Desalin. 2017 Dec;7(4):387-419. [9] Loow YL, New EK, Yang GH, Ang LY, Foo LY, Wu TY. Potential use of deep eutectic solvents to facilitate lignocellulosic biomass utilization and conversion. Cellulose 2017 Sep 1;24(9):3591-618. [10] Abraham E, Deepa B, Pothen LA, Cintil J, Thomas S, John MJ, Anandjiwala R, Narine SS. Environmental friendly method for the extraction of coir fibre and isolation of nanofibre Carbohydr Polym 2013 Feb 15;92(2):1477-83. [11] Wahi R, Ngaini Z, Jok VU. Removal of mercury, lead and copper from aqueous solution by activated carbon of palm oil empty fruit bunch. World Appl Sci J 2009;5(84):84-91. [12] Oboh OI, Aluyor EO. The removal of heavy metal ions from aqueous solutions using sour sop seeds as biosorbent. Afr J Biotechnol 2008; 7(24). [13] Egila JN, Okorie EO. Influence of pH on the Adsorption of trace metals on ecological and agricultural adsorbents. J Chem Soc Niger 2002; 27(11):95-8. [14] Gimba CE, Olayemi JY, Ifijeh DO, Kagbu JA. Adsorption of Dyes by powdered and granulated activated carbon from coconut shell. J Chem Soc Niger 2001; 26(1):23-7. [15] Upatham ES, Boonyapookana B, Kruatrachue M, Pokethitiyook P, Parkpoomkamol K. Biosorption of cadmium and chromium in duckweed Wolffia globosa. Int J Phytorem 2002 Apr 1; 4(2):73-86. [16] Peng BL, Dhar N, Liu HL, Tam KC. Chemistry and applications of nanocrystalline cellulose and its derivatives: a nanotechnology perspective. Can J Chem Eng 2011 Oct; 89(5):1191-206. [17] Šturcová A, Davies GR, Eichhorn SJ. Elastic modulus and stress-transfer properties of tunicate cellulose whiskers. Biomacromolecules 2005 Mar 14;6(2):1055-61. [18] Zhao Y, Zhang Y, Lindström ME, Li J. Tunicate cellulose nanocrystals: preparation, neat films and nanocomposite films with glucomannans Carbohydr Polym 2015 Mar 6;117:286-96. [19] Imai T, Sugiyama J. Nanodomains of Iα and Iβ cellulose in algal microfibrils. Macromolecules 1998 Sep 8;31(18):6275-9. [20] Kim NH, Herth W, Vuong R, Chanzy H. The cellulose system in the cell wall of Micrasterias. J Struct Biol 1996 Nov 1;117(3):195-203. [21] Sugiyama J, Harada H, Fujiyoshi Y, Uyeda N. Lattice images from ultrathin sections of cellulose microfibrils in the cell wall of Valonia macrophysa Kütz. Planta 1985 Oct 1;166(2):161-8. [22] Hua K, Strømme M, Mihranyan A, Ferraz N. Nanocellulose from green algae modulates the in vitro inflammatory response of monocytes/macrophages. Cellulose 2015 Dec 1;22(6):3673-88. [23] Habibi Y, Lucia LA, Rojas OJ. Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 2010 Jun 9;110(6):3479-500. [24] Shak KP, Pang YL, Mah SK. Nanocellulose: Recent advances and its prospects in environmental remediation. Beilstein J Nanotechnol 2018 Sep 19;9(1):2479-98. [25] Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray D, Dorris A. Nanocelluloses: a new family of nature‐based materials. Angew Chem Int Ed 2011 Jun 6;50(24):5438-66.

4154

ISSN- 2394-5125 VOL 7, ISSUE 12, 2020 [26] Du H, Liu C, Mu X, Gong W, Lv D, Hong Y, Si C, Li B. Preparation and characterization of thermally stable cellulose nanocrystals via a sustainable approach of FeCl 3-catalyzed formic acid hydrolysis. Cellulose 2016 Aug 1;23(4):2389-407. [27] De Oliveira FB, Bras J, Pimenta MT, da Silva Curvelo AA, Belgacem MN. Production of cellulose nanocrystals from sugarcane bagasse fibers and pith. Ind Crops Prod 2016 Dec 25;93:48-57. [28] Jonoobi M, Oladi R, Davoudpour Y, Oksman K, Dufresne A, Hamzeh Y, Davoodi R. Different preparation methods and properties of nanostructured cellulose from various natural resources and residues: a review. Cellulose 2015 Apr 1;22(2):935-69. [29] Nechyporchuk O, Pignon F, Belgacem MN. Morphological properties of nanofibrillated cellulose produced using wet grinding as an ultimate fibrillation process. J Mater Sci 2015 Jan 1;50(2):531-41. [30] Naderi A, Lindström T, Sundström J. Repeated homogenization, a route for decreasing the energy consumption in the manufacturing process of carboxymethylated nanofibrillated cellulose?. Cellulose 2015 Apr 1;22(2):1147-57. [31] Taipale T, Österberg M, Nykänen A, Ruokolainen J, Laine J. Effect of microfibrillated cellulose and fines on the drainage of kraft pulp suspension and paper strength. Cellulose 2010 Oct 1;17(5):1005-20. [32] Zhang L, Tsuzuki T, Wang X. Preparation of cellulose nanofiber from softwood pulp by ball milling. Cellulose 2015 Jun 1;22(3):1729-41. [33] Uetani K, Yano H. Nanofibrillation of wood pulp using a high-speed blender. Biomacromolecules 2011 Feb 14;12(2):348-53. [34] Börjesson M, Westman G. Crystalline nanocellulose—preparation, modification, and properties. Cellulose 2015 Dec 9:159-91. [35] Bhatnagar A, Sain M. Processing of cellulose nanofiber-reinforced composites. J Reinf Plast Compos 2005 Aug; 24(12):1259-68. [36] Khoo RZ, Chow WS, Ismail H. Sugarcane bagasse fiber and its cellulose nanocrystals for polymer reinforcement and heavy metal adsorbent: a review. Cellulose 2018 Aug 1;25(8):4303-30. [37] Wulandari WT, Dewi R. Quality Improvement of Used Cooking Oil by Using Nanocellulose from Sugarcane Bagasse as Adsorbent. Molekul 2019 Jun 4;14(1):25-30.

4155