Carbohydrate Polymers 74 (2008) 617620

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Adsorption of sulphate ions by modication of sugarcane bagasse cellulose

Departamento de Materiais e Tecnologia, Faculdade de Engenharia de Guaratinguet, Av. Dr. Ariberto Pereira da Cunha, 12516-410 Guaratinguet, So Paulo, Brazil Departamento de Engenharia Qumica, Escola de Engenharia de Lorena, 12600-000 Lorena, So Paulo, Brazil

a r t i c l e

i n f o

a b s t r a c t
This work describes the preparation of sugarcane bagasse cellulose with zirconium oxychloride for adsorption of sulphate ions in aqueous solution. The materials were prepared by using an ammonium solution as precipitating agent. The obtained materials were characterized by thermogravimetry, scanning electron microscopy and surface area measurements. Sulphate ion was adsorbed on the Cell/ ZrO2nH2O by immersing this solid in an aqueous solution of sulphate sodion. The analyses to determine the concentration after the adsorption were made using UVvis spectrum, in a wavelength of 420 nm. The results were satisfactory showing that the Cell/ZrO2nH2O materials obtained presented good adsorption capacity. The adsorption capacity was 0.4 mol g1 for both materials. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 10 September 2007 Received in revised form 3 April 2008 Available online 16 April 2008 Keywords: Modied sugarcane bagasse Adsorption Cellulose/hydrous zirconium oxide

1. Introduction Sulphate is a major ion occurring in natural waters and wastewaters. The main natural source of sulphate in surface and ground water is the processes of chemical weathering and dissolution of sulphur-containing minerals. Other natural sources are the oxidation of sulphides and elemental sulphur, and the decomposition of animal and plant residues. Sulphur is a nutrient essential for the synthesis of proteins and it is released upon their degradation (Radojevic & Bashkin, 1999). Measurement of sulphate is a crucial step in environmental monitoring, regulatory inspection and compliance, especially in the treatment of mining-inuenced waters. Determination of sulphate is useful in assessing the redox state of the system because sulphur is a critical element in controlling the fate and solubility of polluting elements in the aquatic environmental (Baird, 1995). Sulphate ions are measured using many direct and indirect analytical principles including ion chromatography (IC), inductively coupled plasma absorption spectrophotometry (ICP-AES), turbidimetric, colorimetric and gravimetric methods (Morais, Souto, Lopes, & Rangel, 2003; Reisman, Sundaram, Al-Abed, & Allen, 2007). However, the turbidimetric method is very rapid, where an excess of barium chloride is added to the sample. The barium ion reacts with the sulphate to precipitate barium sulphate. The colloidal suspension is measured using a spectrophotometer and the sulphate concentration determination by comparison with standards (Radojevic & Bashkin, 1999).

* Corresponding author. Tel.: +55 12 31232865; fax: +55 12 31232852. E-mail address: [email protected] (D.R. Mulinari). 0144-8617/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbpol.2008.04.014

Agricultural residues have been used for production starting materials. Reusing and recycling these residues can minimize the environmental problems associated with their build-up reducing the use of noble starting materials. This trend has contributed to the reconsideration of the use of traditional biomaterials such as natural bers to substitute synthetic polymers. Sugarcane bagasse is a residue produced in large quantities by sugar and alcohol industries. According to Cerqueira, Rodrigues Filho, and Meireles (2007), 1 ton of sugarcane generates 280 kg of bagasse and 3 108 tons of sugarcane is processed annually in Brazil. About 80% of this residue is used in distillery plants as a source of energy (Pandey, Soccol, Nigam, & Soccol, 2000). Thus, on account of the importance of bagasse sugarcane as an industrial waste, there is a great interest in developing chemical methods for recycling it. Sugarcane bagasse has around 50% cellulose, 27% polyoses, and 23% lignin. These three biological polymers have many hydroxyl and/or phenolic functions that can be chemically reacted to produce materials with new properties (Pasquini, Belgacem, Gandini, & Curvelo, 2006; Rodrigues Filho et al., 2000; uma, Silva, & Meireles, 2005). Cellulose, the most abundant of all naturally occurring substances, is the principal structural cell wall component of all major plants and accounts for about a half of the total bagasse. It is nontoxic, renewable, biodegradable and modiable, and has great potential as an excellent industrial material. Chemical modication of cellulose is one method for the production of value added products. It is based on reactions of the free hydroxyl groups in the anhydroglucose units, resulting in the production of cellulose derivatives (Karnitz et al., 2007; Liu et al., 2007a,b). Despite many studies of the chemical modication of cellulose published around the world in this area, only a few have been investigated about the modication of sugarcane bagasse (Liu, Sun, Zhang, Ren, & Geng, 2006; Liu et al., 2007a,b).

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In the present work, we describe the chemical modication of sugarcane bagasse cellulose and evaluation to adsorb sulphate ions in aqueous solution. 2. Experimental 2.1. Isolation crude cellulose from sugarcane bagasse To isolate the cellulose, the sugarcane bagasse was pretreated with 10% sulphuric acid solution (reactor of 350 L at 120 C, 10 min), followed by centrifugation with the purpose of separating the rich pentosanes solution. Extracted lignocellulosic fraction was deslignicated with 1% sodium hydroxide solution (reactor of 350 L at 100 C, 1 h) being obtained the crude pulp and bleached with sodium chloride. Furthermore the bleached cellulose dried in a store at 50 C, 12 h (Rocha, 2000). 2.2. Preparation of the hydrous zirconium oxide Five grams of zirconium oxychloride were dissolved in 100 mL of aqueous hydrochloric acid solution (0.5 mol L1). The precipitate was obtained adding an ammonium solution (1:3) at pH 10.0, under stirring, which was ltered, rinsed several times with distilled water for the complete removal of chloride ions (negative silver nitrate test). Finally, the product was dried at 50 C for 24 h. 2.3. Preparation of the cellulose/hydrous zirconium oxide hybrid materials About 2 g of zirconium oxychloride were dissolved in 100 mL of aqueous hydrochloric acid solution (0.5 mol/L) and 5 g of cellulose were immersed in this solution. The material was precipitate with ammonium solution (1:3) at pH 10.0 and under stirring. The solid after being exhaustively washed with distilled water and the residual solvent was removed under vacuum. The product was dried at 50 C for 24 h. The resulting material was designated as Cell/ZrO2nH2O (2 g). The preparation was repeated using the same procedure, but changing the amount of the metal oxide precursor reagent, i.e., 3 g of zirconium oxychloride. 2.4. Adsorption sulphate ions in the cellulose/hydrous zirconium oxide hybrids materials About 0.2 g of Cell/ZrO2nH2O material was shapen for 5 min at 298 K in 50 mL of Na2SO4 solution whose initial concentrations varied between 0.5.104 and 5.104 mol L1. The amount of sulphate in the supernatant solution was determined using turbidimetric method by UVvis absorption spectra, in the wavelength at 420 nm. The amount of adsorbed sulphate ions was determined by applying the equation Pavan, Francisco, Landers, & Gushikem 2005): Nf Ni Ns m 1

rate of 20 C min1 in N2 atmosphere. Surface area measurements (BET) were obtained in a Quantachrome instrument model NOVA 1000 in nitrogen atmosphere, followed by pre-treatment at 50 C for 3 h of samples. Micrographs (SEM) were obtained in a scanning electron microscope LEO1450 V using low vacuum, in backscattered electrons for the cellulose and hybrids materials. Samples were dispersed on a brass support and xed with a double face 3 M tape. 3. Results and discussion Cell/ZrO2nH2O hybrids materials were obtained with a satisfactory degree of coated with oxide on the cellulose surface. The amount of ZrO2nH2O incorporated into the Cell/ZrO2nH2O hybrids materials were determined calcining 0.3 g of sample at 1173 K in air for 3 h and weighing the residue (Table 1). The deposited hydrous zirconium oxide is amorphous because the specic surface area, SBET, increased from 0 m2 g1 (see Table 1) in pure cellulose to 57 m2 g1 for the material Cell/ZrO2nH2O. These effects can be conrmed by TG curves. TG curves obtained of materials are presented in Fig. 1. Curve 1A corresponds to bleached cellulose, curve 1B to hydrous zirconium oxide and curves 1C and 1D to the hybrids materials. Bleached cellulose present two decomposition steps: rst at 300 C corresponds to degradation temperature and second one at 380 C corresponds to decomposition temperature completed. Cell/ZrO2nH2O (2 g) hybrids materials show two different steps in relation to bleached cellulose: one at 260 C and the other one at around 338 C. Cell/ ZrO2nH2O (3 g) is similar to Cell/ZrO2nH2O (2 g). This progressive decrease in temperature of hybrids materials in relation to bleached cellulose may be attributed to the presence of the dispersed oxide particles on cellulose surface, indicating a strong interaction between hydrous zirconium oxide and cellulose bers The condition of the preparation of hybrid materials (acid medium at the beginning and basic medium in the end) did not degrade the cellulose ber, because it is known that the cellulose degradation

Table 1 Quantity of ZrO2nH2O incorporated on cellulose surface Samples Cellulose ZrO2nH2O Cell/ ZrO2nH2O (2 g) Cell/ ZrO2nH2O (3 g) ZrO2nH2O incorporated (wt%) 3.66 5.45 SBET (m2/g) 0 254 36 57

where Ni and Ns are the initial and equilibrium condition mol number of sulphate sodium and m is mass of the solid. 2.5. Characterization of the materials The materials were characterized by thermogravimetry, scanning electron microscopy and surface area measurements. Thermogravimetry (TG) measurements were obtained in a Shimadzu thermogravimetric instrument model TGA-50. Thermal behavior for each one of the preparations was studied by recording the TG/DTG curves between 40 and 800 C rates under nitrogen atmosphere using weighted samples between 5 and 10 mg with a heat

Fig. 1. TG curves: (A) pure cellulose; (B) ZrO2nH2O; (C) Cell/ZrO2nH2O (2 g); (D) Cell/ZrO2nH2O (3 g).

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occurs at pH 10 (Borgo & Gushikem, 2002). Due to this, during the process, care was taken not to pass this pH. (Mulinari, Da Silva, & Da Silva 2006). Toledo, Gushikem, and Castro (2000) studied the antimony (III) oxide lm on a cellulose ber surface and it was observed similar results. Table 2 shows the values of percentage mass loss in the respective temperature range and residue occurred in the materials. TG curve of the pure cellulose presents a higher mass loss in relation to the hybrids materials in temperature range 200 500 C, due to the presence of metallic oxide in the cellulose surface. Comparing TG curves of the pure cellulose with of hydrous metallic oxide in this temperature range, was observed that the oxide present a lesser mass loss in relation the pure cellulose, therefore the pure cellulose was practically all degraded while that the oxide presented a 71% residue. It was also observed that the amount of residue in the hybrids materials increased, due to the amount of ZrOCl28H2O in the reactional system. The residue of each hybrid material presents the amount of oxide which was not degraded. By means of the TG curves can be calculated the amount of grafted material in hybrids materials. Table 3 shows the percentages of ZrO2nH2O grafted in the cellulose, being that the loss mass corresponds to the interval of 200300 C (see Fig. 1), where occurred higher loss mass. It was also observed that the Cell/ZrO2nH2O (3 g) presented a higher grafted that the Cell/ZrO2nH2O (2 g) with an increase of approximately 92%. The results were conrmed by scanning electron microscope (SEM). The bleached cellulose micrograph (Fig. 2A) shows a great amount of bers presents forms attened while the hydrous zirconium oxide (Fig. 2B) presents as a porous agglomerates. Fig. 2C and D shows the hydrous zirconium oxide dispersed on the surface of the bers cellulose. However, it is noticed that the oxide was not deposited of a uniform way on the surface bers cellulose. As expected, it was observed an increase of oxide in the Cell/ZrO2nH2O (3 g) (Fig. 2D). After the characterization of materials, it was determined the amount of sulphate ions incorporated on the Cell/ZrO2nH2O hybrids materials surface. Figs. 3 and 4 show the adsorption isotherm of sulphate ions on the Cell/ZrO2nH2O hybrids materials surface, determined at 298 K.

Table 2 Results of the thermogravimetrics curves of the materials, with the losses mass (m), in the respective range of temperature (DT) and its respective residues (R) Material Cellulose m (%) 4.7 83.9 8.6 28.3 0.6 7.1 77.7 2.9 9.7 64.3 6.9 DT (C) 40200 200500 500800 40500 500800 40200 200500 500800 40200 200500 500800 R (%) 2.8

ZrO2nH2O Cell/ZrO2nH2O (2 g)

71.1 12.3

Cell/ZrO2nH2O (3 g)

19.1

Table 3 Percentages of grafted materials in the Cell/ZrO2nH2O Material Cell/ZrO2nH2O (2 g) Cell/ZrO2nH2O (3 g) Initial mass (mg) 4.2 5.0 Loss mass (mg) 3.3 3.2 Final mass (mg) 0.9 1.8 Grafted material (%) 29 55 Fig. 2. Micrographs: (A) pure cellulose; (B) ZrO2nH2O; (C) Cell/ZrO2nH2O (2 g); (D) Cell/ZrO2nH2O (3 g).

At the limit of saturation of the surface, the maximum adsorption capacity of sulphate ions was 0.4 mol g1 for both materials.

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0.45 0.40 0.35 0.30

lulose ber surface. However the metal oxide was heterogeneously dispersed on the cellulose ber surface. These results were conrmed by characterization techniques. The results obtained for adsorption capacity from solutions of sulphate sodium, that both Cell/ZrO2nH2O hybrids materials showed good adsorption capacity. Acknowledgement

Nf (mol/g)

0.25 0.20 0.15 0.10 0.05 0

The authors express their acknowledgements to CAPES for the nancial support. References
Baird, C. (1995). Environmental chemistry. New York: W.H. Freeman and Company. Borgo, C. A., & Gushikem, Y. (2002). Zirconium phosphate dispersed on a cellulose ber surface: preparation, characterization, and selective adsorption of Li+, Na+ and K+ from aqueous solution. Journal of Colloid and Interface Science, 246, 343347. Cerqueira, D. A., Rodrigues Filho, G., & Meireles, C. S. (2007). Optimization of sugarcane bagasse cellulose acetylation. Carbohydrate Polymers, 69, 579582. Da Silva, G. L. J. P., Da Silva, M. L. C. P., & Caetano, T. (2002). Preparation and characterization of hydrous zirconium oxide formed by homogeneous precipitation. Materials Research, 5, 149153. Karnitz, O., Jr., Gurgel, L. V. A., Melo, J. C. P., Botaro, V., Melo, T. M. S., Gil, R. P. F., et al. (2007). Adsorption of heavy metal ion from aqueous single metal solution by chemically modied sugarcane bagasse. Bioresource Technology, 98, 12911297. Liu, C. F., Sun, R. C., Zhang, A. P., Ren, J. L., & Geng, Z. C. (2006). Structural and thermal characterization of sugarcane bagasse cellulose succinates prepared in ionic liquid. Polymer Degradation and Stability, 91, 30403047. Liu, C. F., Sun, R. C., Zhang, A. P., Ren, J. L., Wang, X. A., Qin, M. H., et al. (2007a). Homogeneous modication of sugarcane bagasse cellulose with succinic anhydride using an ionic liquid as reaction medium. Carbohydrate Research, 342, 919926. Liu, C. F., Suna, R. C., Qin, M. H., Zhang, A. P., Ren, J. L., Xu, F., et al. (2007b). Chemical modication of ultrasound-pretreated sugarcane bagasse with maleic anhydride. Industrial Crops and Products, 26, 212219. Morais, I. P. A., Souto, M. R. S., Lopes, T. I. M. S., & Rangel, A. O. S. S. (2003). Use of a single air segment to minimise dispersion and improve mixing in sequential injection: Turbidimetric determination of sulphate in waters. Water Research, 37, 42434249. Mulinari, D. R., Da Silva, M. L. P., & Da Silva, G. L. J. P. (2006). Adsorco de ons dicromato nos compsitos cellulose/ZrO2nH2O preparados pelos mtodos da precipitaco convencional e em soluco homognea. Qumica Nova, 29, 496500. Pandey, A., Soccol, C. R., Nigam, P., & Soccol, V. T. (2000). Biotechnological potential of agro-industrial residues: I. Sugarcane bagasse.. Biosource Technology, 74, 6980. Pasquini, D., Belgacem, M. N., Gandini, A., & Curvelo, A. A. S. (2006). Surface esterication of cellulose bers: Characterization by DRIFT and contact angle measurements. Journal of Colloid and Interface Science, 295, 7983. Pavan, F. A., Francisco, M. S. P., Landers, R., & Gushikem, Y. (2005). Adsorption of phosphoric acid niobium oxide coated cellulose ber: Preparation, characterization and ion exchange property. Journal Brazilian Chemistry Society, 16, 815820. Peixoto, A. L. C., Da Silva, G. L. J. P., & Da Silva, M. L. C. P. (2006). Estudo da temperatura na sntese de xidos hidratados de nibio e zircnio e adsorco de ons Ag+ e Pb2+. Cermica, 52, 249254. Radojevic, M., & Bashkin, V. N. (1999). Practical environmental analysis. Cornwall, UK: MPG Books Ltd., Bodmin. Reisman, D. J., Sundaram, V., Al-Abed, S. R., & Allen, D. (2007). Statistical validation of sulfate quantication methods used for analysis of acid mine drainage. Talanta, 71, 303311. Rocha, G. J. M. (2000). Deslignicaco de Bagaco de Cana de Accar Assistida por Oxignio. Tese de Doutorado, Universidade Federal de So Carlos. Rodrigues Filho, G., Cruz, S. F., Pasquini, D., Cerqueira, D. A., Prado, V. S., & Assunco, R. M. N. (2000). Water ux through cellulose triacetate lms produced from heterogeneous acetylation of sugar cane bagasse. Journal of Membrane Science, 177, 225231. Rodrigues Filho, G., Silva, R. C., & Meireles, C. S. (2005). Water ux trough blends from waste materials: Cellulose acetate (from sugar cane bagasse) with polystyrene (from plastic cups). Journal of Applied Polymer Science, 96, 516522. Suzuki, T. M., Bomani, J. O., Matsunaga, H., & Yokoyama, T. (2000). Preparation of porous resin loaded with crystalline hydrous zirconium oxide and its application to the removal of arsenic. Reactive & Functional Polymers, 43, 165172. Toledo, E. A., Gushikem, Y., & Castro, S. C. (2000). Antimony (III) oxide lm on a cellulose ber surface: Preparation and characterization of the composite. Journal of Colloid and Interface Science, 225, 455459.

Na2 SO4(mol/L)
Fig. 3. Adsorption of sulphate ions on the Cell/ZrO2nH2O (2 g).

0.45

0.40

0.35

0.30

N f (mol/g)

0.25

0.20

0.15

0.10 0 1 2 3 4 5

Na 2 SO4(mol/L)
Fig. 4. Adsorption of sulphate ions on the Cell/ZrO2nH2O (3 g).

Under such conditions, assuming that all the ZrO2 particles dispersed on the cellulose surface reacted with sulphate ions, the adsorption process may occur by reaction of sulphate ions and the zirconium reactive center, designated as Zr-OH, can be expressed as follows (Suzuki, Bomani, Matsunaga, & Yokoyama 2000): Protonation at lower pH Cell=ZrOHsol H ! Cell=ZrOH 2 Followed by bonding of a sulphate ion Cell=ZrOH SO2 ! Cell=ZrOH SO2 2 4 2 4 3 2

Analyzing the results it was observed that both Cell/ZrO2nH2O hybrids materials presented good adsorption capacity. As the Cell/ ZrO2nH2O hybrids materials showed close specic surface area (see Table 1), it was expected the materials to present similar adsorption capacity, since the adsorption capacity is related to specic surface area (Da Silva, Da Silva, & Caetano 2002; Peixoto, Da Silva, & Da Silva 2006). 4. Conclusions The hybrids materials Cell/ZrO2nH2O were obtained with a high degree of dispersion with hydrous zirconium oxide on the cel-